Photocrosslinkable Materials

ABSTRACT

A diamine compound of formula (I) is proposed as well as polymers, copolymers, polyamic acids, polyamic acid esters, or polyimides based on such compound.

The invention relates to diamine compounds, represented by the generalformula (I), and also relates to oligomers, polymers and copolymers fromthe class of polyamic acids, polyamic acid esters or polyimides (and anymixtures thereof) obtained by the reaction of a diamine compoundrepresented by the general formula (I) and optionally of one or moreadditional other diamines, with one or more tetracarboxylic acidanhydrides, and to the use of these diamine compounds, oligomers,polymers and copolymers for the preparation of orientation layers forliquid crystals and in the construction of unstructured and structuredoptical elements and multi-layer systems.

Liquid crystal displays (LCDs) are becoming increasingly dominant inadvanced visualization devices. LCDs offer favourable characteristicswith respect to image quality (high luminance, high resolution, colourand grey scale capability), power consumption as well as dimensions andweight (flat panel displays). The use of commercial LCDs has becomewidespread, e.g. in automotive and telecommunication instruments, aswell as in monitors of notebooks, desktop computers, television sets,etc. Today the need for LCDs in television applications is rapidlygrowing. Recently developed LCD modes possess high potentials inachieving fast response times, wide viewing angles and high luminance.Amongst other newly developed LCD modes, the MVA (multi-domain verticalalignment) mode appears to be the most promising for the use in moderntelevision applications.

In the MVA mode the liquid crystal molecules are usually nearlyvertically aligned with respect to the surface of the substrates. Byusing protrusions (or other alignment subdivisions) on the surface ofthe substrate, the liquid crystal molecules become locally pre-tiltedwithin a single cell in more than one direction, leading to domainsswitchable in different directions. This multi-domain configurationexhibits very good display performance, with wide viewing angles of upto 160° in any direction, short response times (below 20 ms), highcontrast ratios (up to 700:1) and high brightness. However, by means ofusing protrusions only, it is difficult to clearly define the domainspace within a single pixel. Therefore the MVA mode demands additionalmanufacturing steps to ensure shape effects as well as electrical fieldeffects on both the upper and lower substrate; hence all in all leadingto complex manufacturing procedures.

In order to by-pass this technical challenge, the availability of analignment layer would be desirable, which directly leads to pre-definedalignment directions within each pixel domain and having wellcontrollable off-axis angles with respect to the normal axis of thesubstrate.

Methods for the preparation of orientation layers for liquid crystalmaterials are well known to the skilled person. Customarily useduniaxially rubbed polymer orientation layers, such as for examplepolyimides, however, do have a series of disadvantages, like theformation and deposition of dust during the rubbing process andconcomitant partial destruction of the thin film transistors. Scratchesdue to brushing is another issue associated with this technique, whichis particularly evident when the pixels are of the order of 10 micronsor even lower, like e.g. in micro-display applications. Because of thestrong optical magnification, which is required to visualize thedisplayed information, scratches easily become visible and are also thecause for the reduction of the contrast level. Furthermore, the rubbingprocess does not allow the production of structured layers.

The production procedure for obtaining orientation layers in which thedirection of orientation is induced by irradiation with polarized lightis not faced with the problems inherent to the rubbing process. With theirradiation technique it is furthermore also possible to create areashaving different orientation and thus to structure the orientation layeras described for example in Jpn. J. Appl. Phys., 31 (1992), 2155-64(Schadt et al).

Using the linearly photo-polymerizable alignment (LPP) technique, thepossibility of realizing a four-domain vertical aligned nematic (VAN)LCD was demonstrated some years ago (K. Schmitt, M. Schadt; Proceedingsof EuroDisplay 99, 6-9 Sep., 1999). The four-domain VAN-LCD exhibits anexcellent off-state angular brightness performance.

Apart from the current display performance requirements to be fulfilledin modern TV applications, the use of appropriate LPP materials isfurthermore also guided by the necessity to achieve specific optical andelectro-optical properties, e.g. with respect to the compatibility withthe TFT (thin film transistors). Other important characteristics of thematerials must also be taken into consideration, i.e. those crucialparameters directly related to and dependent on the molecular propertiesof the material.

Primarily such characteristics are:

-   -   High voltage holding ratio (VHR), i.e. VHR of >90% (measured at        80° C.)    -   High stability of the induced pre-tilt angle against light and        heat    -   Low alignment energy profile (short irradiation time and/or low        irradiation energy)

In the case of LCDs of thin-film transistor type a certain amount ofcharge is applied over the course of a very short period of time to theelectrodes of a pixel and must not subsequently drain away by means ofthe resistance of the liquid crystal. The ability to hold that chargeand thus to hold the voltage drop over the liquid crystal is quantifiedby what is known as the “voltage holding ratio” (VHR). It is the ratioof the RMS-voltage (root mean square voltage) at a pixel within oneframe period and the initial value of the voltage applied.

Photo-reactive materials for orientation layers with improved voltageholding ratios (VHR) are described in WO-A-99/49360, U.S. Pat. No.6,066,696, U.S. Pat. No. 6,027,772, WO-A-99/15576 and WO-A-99/51662. InWO-A-99/49360, U.S. Pat. No. 6,066,696 and U.S. Pat. No. 6,027,772blends of polymeric compounds are described, containing photo-reactivepolymers and polyimides.

In WO-A-99/15576 and WO-A-99/51662 polyimides having photo-reactivecinnamate groups incorporated in their side chains are described.WO-A-99/15576 for instance discloses photo-active polymers which containas side-chain specific photo-cross-linkable groups and of which atypical monomer unit is6-{2-methoxy-4-[(1E)-3-methoxy-3-oxoprop-1-enyl]phenoxy}hexyl3,5-diaminebenzoate.

In the above cited references it was generally demonstrated that inorder to achieve the aforementioned important parameters, molecularstructures combining firstly a polyamic/polyimide backbone (i.e.delivering molecular polarity) and secondly side chains with anincorporated photo-reactive group, such as a cinnamic acid residue, aresuitable for the general concept of planar orientation [requiring onlyslight pretilt angles, like e.g. being used in TN (twisted nematic)devices]. However, these types of molecular structures, primarilydeveloped for TN applications, cannot directly be utilized in MVAapplications.

Thus, the present invention relates to diamine compound of formula (I):

wherein,

-   A represents an unsubstituted or substituted carbocyclic or    heterocyclic aromatic group selected from a monocyclic ring of five    or six atoms, two adjacent monocyclic rings of five or six atoms, a    bicyclic ring system of eight, nine or ten atoms, or a tricyclic    ring system of thirteen or fourteen atoms;    and    wherein the following compound residue of formula (I), the compound    residue (Ia)

represents a straight-chain or branched C₁-C₁₆fluoralkyl group, wherein

-   F is fluorine, and-   x₁ is an integer from 1 to 15, preferably an integer from 1 to 10;    more preferably 1, 2, 3, 4, 5, 6, 7, 8 or 9 and most preferred 3, 4,    5 or 7;-   B represents a straight-chain or branched C₁-C₁₆alkyl group, which    is in addition to its fluorine substituent(s) unsubstituted or    substituted by di-(C₁-C₁₆alkyl)amino, C₁-C₆alkyloxy, nitro, cyano    and/or chlorine; and wherein one or more —CH₂— group may    independently from each other be replaced by a linking group;-   D represents an unsubstituted or substituted, aliphatic, aromatic    and/or alicyclic diamine group having from 1 to 40 carbon atoms;-   preferably D represents an unsubstituted or substituted, aliphatic,    aromatic and/or alicyclic diamine group having from 1 to 40 carbon    atoms, wherein the diamine group comprises an aliphatic group, which    may comprise one or more heteroatom and/or bridging group;    -   and/or an aromatic group;    -   and/or an alicyclic group;-   E represents an aromatic group, an oxygen atom, a sulphur atom,    —NH—, —N(C₁-C₆alkyl)-, —CR²R³,    -   wherein R² and R³ are independently from each other hydrogen or        a cyclic, straight-chain or branched, substituted or        unsubstituted C₁-C₂₄alkyl, wherein one or more —CH₂— group(s)        may be independently from each other replaced by a linking        group, and with the proviso that at least one of R² and R³ is        not hydrogen;-   S¹, S² each independently from each other represents a spacer unit;-   X, Y each independently from each other represents hydrogen,    fluorine, chlorine, cyano, unsubstituted or with fluorine    substituted C₁-C₁₂alkyl, in which one or more —CH₂— groups may be    replaced by a linking group;    n, n1 each independently from each other represents 1, 2, 3 or 4,    preferably n1 is 1 and n is 1 or 2;    with the proviso that if n is 2, 3, or 4, each A, B, x₁, E, S¹, S²,    X, Y are identical or different; and if n1 is 2, 3 or 4 each B, x₁    is identical or different;    preferably,    wherein, if n>1, compound (I) has several side-chains [wherein    side-chain has the meaning of structures (I) without the group D],    which are linked to residue D at one atomic position within group D,    e.g. two or three side chains linked to one single carbon atom    within group D, or they can be linked to group D at different atomic    positions within group D, e.g. at adjacent atomic positions within    group D, or/and they can linked spaced further apart.

In a preferred embodiment the present invention relates to Diaminecompound of formula (I):

wherein,

-   A represents a unsubstituted or substituted carbocyclic or    heterocyclic aromatic group selected from a monocyclic ring of five    or six atoms, two adjacent monocyclic rings of five or six atoms, a    bicyclic ring system of eight, nine or ten atoms, or a tricyclic    ring system of thirteen or fourteen atoms;-   F is fluorine, and-   x₁ is an integer from 1 to 15,-   B represents a straight-chain or branched C₁-C₁₆alkyl, which is    unsubstituted or substituted by di-(C₁-C₁₆alkyl)amino,    C₁-C₆alkyloxy, nitro, cyano and/or chlorine or fluorine; and wherein    one or more —CH₂— group may independently be replaced by a linking    group;-   D represents unsubstituted or substituted aliphatic, aromatic or    alicyclic diamine group having from 1 to 40 carbon atoms,-   E represents an aromatic group, an oxygen atom, a sulphur atom,    —NH—, —N(C₁-C₆alkyl)-, —CR²R³,    -   wherein R² and R³ are independently from each other hydrogen or        a cyclic, straight-chain or branched, substituted or        unsubstituted C₁-C₂₄alkyl, wherein one or more —CH₂— groups may        be replaced by a linking group, and with the proviso that at        least one of R² and R³ is not hydrogen;-   S¹, S² each independently from each other represents a spacer unit;-   X, Y each independently from each other represents hydrogen,    fluorine, chlorine, cyano, unsubstituted or with fluorine    substituted C₁-C₁₂alkyl, in which one or more —CH₂— groups may be    replaced by a linking group;-   n is 1, 2, 3 or 4,    -   with the proviso that if n is 2, 3, or 4, each A, B, x₁, D, E,        S¹, S², X, Y may be identical or different.

The term “linking group”, as used in the context of the presentinvention is preferably be selected

from —O—, —CO, —CO—O—, —O—CO—,

—NR¹—, —NR¹—CO—, —CO—NR¹—, —NR¹—CO—O—, —O—CO—NR¹—, —NR¹—CO—NR¹—,—CH═CH—, —C≡C—, —O—CO—O—, and —Si(CH₃)₂—O—Si(CH₃)₂—, and wherein:

-   R¹ represents a hydrogen atom or C₁-C₆alkyl;    with the proviso that oxygen atoms of linking groups are not    directly linked to each other.

The term “spacer unit” as used in the context of the present invention,is preferably a single bond, a cyclic, straight-chain or branched,substituted or unsubstituted C₁-C₂₄alkylen, wherein one or more,preferably non-adjacent, —CH₂— groups may independently from each otherbe replaced by a linking group as described above and/or a non-aromatic,aromatic, unsubstituted or substituted carbocyclic or heterocyclic groupconnected via bridging groups.

More preferably, the spacer unit is a cyclic, straight-chain orbranched, substituted or unsubstituted C₁-C₂₄alkylen, wherein one ormore, preferably non-adjacent, —CH₂— groups may independently from eachother be replaced by a linking group and/or a non-aromatic, aromatic,unsubstituted or substituted carbocyclic or heterocyclic group connectedvia bridging groups.

A bridging group as used in the context of the present invention ispreferably selected from —CH(OH)—, —CO—, —CH₂(CO)—, —SO—, —CH₂(SO)—,—SO₂—, —CH₂(SO₂)—, —COO—, —OCO—, —COCF₂—, —CF₂CO, —S—CO—, —CO—S—, —SOO—,—OSO—, —SOS—, —O—CO—O—, —CH₂—CH₂—, —OCH₂—, —CH₂O—, —CH═CH—, —C≡C—,—CH═CH—COO—, —OCO—CH═CH—, —CH═N—, —C(CH₃)═N—, —N═N— or a single bond; ora cyclic, straight-chain or branched, substituted or unsubstitutedC₁-C₂₄alkylen, wherein one or more —CH₂— groups may independently fromeach other be replaced by a linking group as described above.

Alkyl, alkyloxy, alkylcarbonyloxy, acryloyloxyalkoxy, acryloyloxyalkyl,acryloyloxyalken, alkyloxycarbonyloxy, alkylacryloyloxy,methacryloyloxyalkoxy, methacryloyloxyalkyl, methacryloyloxyalken,alkylmethacryloyloxy, alkylmethacryloyloxy, alkylvinyl, alkylvinyloxyand alkylallyloxy and alkylene, as used in the context of the presentinvention denote with their alkyl residue, respectively their alkyleneresidue, a cyclic, straight-chain or branched, substituted orunsubstituted alkyl, respectively alkylene, in which one or more,preferably non-adjacent, —CH₂— group may be replaced by a linking group.

Further, the alkyl residue is for example C₁-C₄₀alkyl, especiallyC₁-C₃₀alkyl, preferably C₁-C₂₀alkyl, more preferably C₁-C₁₆alkyl, mostpreferably C₁-C₁₀alkyl and especially most preferably C₁-C₆alkyl.Accordingly alkylen is for example C₁-C₄₀alkylen, especiallyC₁-C₃₀alkylen, preferably C₁-C₂₀alkylen, more preferably C₁-C₁₆alkylen,most preferably C₁-C₁₀alkylen and especially most preferablyC₁-C₆alkylen.

In the context of the present invention the definitions for alkyl givenbelow, are applicable to alkylene in analogy.

C₁-C₆alkyl is for example methyl, ethyl, propyl, isopropyl, butyl,sec.-butyl, tert.-butyl, pentyl or hexyl.

C₁-C₁₀alkyl is for example methyl, ethyl, propyl, isopropyl, butyl,sec.-butyl, tert.-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl.

C₁-C₁₆alkyl is for example methyl, ethyl, propyl, isopropyl, butyl,sec.-butyl, tert.-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl or hexadecyl.

C₁-C₂₀alkyl is for example methyl, ethyl, propyl, isopropyl, butyl,sec.-butyl, tert.-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nondecyl, eicosyl.

C₁-C₂₄alkyl is for example methyl, ethyl, propyl, isopropyl, butyl,sec.-butyl, tert.-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nondecyl, eicosyl.

C₁-C₃₀alkyl is for example methyl, ethyl, propyl, isopropyl, butyl,sec.-butyl, tert.-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nondecyl, eicosyl, heneicosyl, tricosyl,tetracosy, pentacosyl, hexacosdy, heptacosyl, octacosyl, nonacosy ortriacontyl.

C₁-C₄₀alkyl is for example methyl, ethyl, propyl, isopropyl, butyl,sec.-butyl, tert.-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nondecyl, eicosyl, heneicosyl, tricosyl,tetracosy, pentacosyl, hexacosdy, heptacosyl, octacosyl, nonacosy,triacontyl or tetracontyl.

C₁-C₂₀acryloyloxyalkylene, prefererably C₁-C₁₀acryloyloxyalkylene, C₁-C₆acryloyloxyalkylene is for example acryloyloxymethylen,acryloyloxyethylene, acryloyloxypropylene, acryloyloxyisopropylene,acryloyloxybutylene, acryloyloxy-sec.-butylene, acryloyloxypentylene,acryloyloxyhexylene, acryloyloxyheptylene, acryloyloxyoctylene,acryloyloxynonylene, acryloyloxydecylene, acryloyloxyundecylene,acryloyloxydodecane, acryloyloxytridecylene, acryloyloxytetradecylene,acryloyloxypentyldecane, acryloyloxyhexadecylene,acryloyloxyheptadecylene, acryloyloxyoctadecylene,acryloyloxynondecylene, acryloyloxyeicosylene.

C₁-C₂₀methacryloyloxyalkylene, prefererablyC₁-C₁₀methacryloyloxyalkylene, C₁-C₆ methacryloyloxyalkylene is forexample methacryloyloxymethylen, methacryloyloxyethylene,methacryloyloxypropylene, methacryloyloxyisopropylene,methacryloyloxybutylene, methacryloyloxy-sec.-butylene,methacryloyloxypentylene, methacryloyloxyhexylene,methacryloyloxyheptylene, methacryloyloxyoctylene,methacryloyloxynonylene, methacryloyloxydecylene,methacryloyloxyundecylene, methacryloyloxydodecane,methacryloyloxytridecylene, methacryloyloxytetradecylene,methacryloyloxypentyldecane, methacryloyloxyhexadecylene,methacryloyloxyheptadecylene, methacryloyloxyoctadecylene,methacryloyloxynondecylene, methacryloyloxyeicosylene.

C₁-C₂₀acryloyloxyalkoxy, preferably C₁-C₁₀acryloyloxyalkoxy, C₁-C₆acryloyloxyalkoxy is for example acryloyloxymethoxy, acryloyloxyethoxy,acryloyloxypropoxy, acryloyloxyisopropoxy, acryloyloxybutoxy,acryloyloxy-sec.-butoxy, acryloyloxypentoxy, acryloyloxyhexoxy,acryloyloxyheptoxy, acryloyloxyoctoxy, acryloyloxynonoxy,acryloyloxydecoxy, acryloyloxyundecoxy, acryloyloxydodecanoxy,acryloyloxytridecyloxy.

C₁-C₂₀methacryloyloxyalkoxy, preferably C₁-C₁₀methacryloyloxyalkoxy,C₁-C₆ methacryloyloxyalkoxy is for example methacryloyloxymethoxy,methacryloyloxyethoxy, methacryloyloxypropoxy,methacryloyloxyisopropoxy, methacryloyloxybutoxy,methacryloyloxy-sec.-butoxy, methacryloyloxypentoxy,methacryloyloxyhexoxy, methacryloyloxyheptoxy, methacryloyloxyoctoxy,methacryloyloxynonoxy, methacryloyloxydecoxy, methacryloyloxyundecoxy,methacryloyloxydodecanoxy, methacryloyloxytridecyloxy.

An aliphatic group is for example a saturated or unsaturated, mono-,bi-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, deca-valentalkyl, alkylene, alkyloxy, alkylcarbonyloxy, acryloyloxy, alkylacryl,alkylmethacryl, alkyl(en)acryl(en), alkyl(en)methacryl(en),alkyloxycarbonyloxy, alkyloxycarbonyloxy methacryloyloxy, alkylvinyl,alkylvinyloxy or alkylallyloxy, which may comprise one or moreheteroatom and/or bridging group.

An alicyclic group is preferably a non-aromatic group or unit.Preferably an alicyclic group is a non-aromatic carbocyclic orheterocyclic group and represents for example ring systems, with 3 to 30carbon atoms, as for example cyclopropane, cyclobutane, cyclopentane,cyclopentene, cyclohexane, cyclohexene, cyclohexadiene, decaline,tetrahydrofuran, dioxane, pyrrolidine, piperidine or a steroidalskeleton such as cholesterol.

The term “aromatic”, as used in the context of the present invention,preferably denotes unsubstituted or substituted carbocyclic andheterocyclic groups, incorporating five, six, ten to 14 ring atoms, e.g.furan, benzene or phenylene, pyridine, pyrimidine, naphthalenen, whichmay form ring assemblies, such as biphenylene or triphenylen, which areuninterrupted or interrupted by at least a single heteroatom and/or atleast a single bridging group; or fused polycyclic systems, such asphenanthrene, tetraline. Preferably aromatic group are benzene,phenylene, biphenylene or triphenylen. More preferred aromatic group arebenzene, phenylene and biphenylene.

A carbocyclic or heterocyclic aromatic group incorporates preferablyfive, six, ten or 14 ring atoms, as for example furan, benzene,pyridine, triazine, pyrimidine, naphthalene, phenanthrene, biphenyleneor tetraline units, preferably naphthalene, phenanthrene, biphenylene orphenylene, more preferably naphthalene, biphenylene or phenylene, andmost preferably phenylene.

The carbocyclic or heterocyclic aromatic group is for exampleunsubstituted or mono- or poly-substituted. Preferred substitutents ofcarbocyclic or heterocyclic aromatic groups are at least one halogen,hydroxyl, a polar group, acryloyloxy, alkylacryloyloxy, alkoxy,alkylcarbonyloxy, alkyloxycarbonyloxy, alkyloxocarbonyloxy,methacryloyloxy, vinyl, vinyloxy and/or allyloxy group, wherein thealkyl residue has preferably from 1 to 20 carbon atoms, and morepreferably having from 1 to 10 carbon atoms. Preferred polar groups arenitro, cyano or a carboxy group, and/or a cyclic, straight-chain orbranched C₁-C₃₀alkyl, which is unsubstituted, mono- or poly-substituted.Preferred substitutents of C₁-C₃₀alkyl are methyl, fluorine and/orchlorine, wherein one or more, preferably non-adjacent, —CH₂— group mayindependently of each other be replaced by a linking group. Preferably,the linking group is selected from —O—, —CO—, —COO— and/or —OCO—.

A monocyclic ring of five or six atoms is for example furan, benzene,preferably phenylene, pyridine, pyrimidine.

A bicyclic ring system of eight, nine or ten atoms is for examplenaphthalene, biphenylene or tetraline.

A tricyclic ring system of thirteen or fourteen atoms is for examplephenanthrene.

The term “phenylene”, as used in the context of the present invention,preferably denotes a 1,2-, 1,3- or 1,4-phenylene group, which isoptionally substituted. It is preferred that the phenylene group iseither a 1,3- or a 1,4-phenylene group. 1,4-phenylene groups areespecially preferred.

The term “halogen” denotes a chloro, fluoro, bromo or iodo substituent,preferably a chloro or fluoro substituent.

The term “polar group”, as used in the context of the present inventionprimarily denotes a group like a nitro, cyano, or a carboxy group.

The term “heteroatom”, as used in the context of the present inventionprimarily denotes oxygen, sulphur and nitrogen, preferably oxygen andnitrogen, in the latter case preferably in the form of —NH—.

The term “optionally substituted” as used in the context of the presentinvention primarily means substituted by lower alkyl, such asC₁-C₆alkyl, lower alkoxy, such as C₁-C₆alkoxy, hydroxy, halogen or by apolar group as defined above.

The term “diamine” or “diamine compound” is to be understood asdesignating a chemical structure which has at least two amino groups,i.e. which may also have 3 or more amino groups. The at least two aminogroups are preferably able to react with e.g. anhydrides as outlined inmore detail below.

The term “dinitro” or “dinitro compound” is to be understood asdesignating a chemical structure which has at least two nitro groups,i.e. which may also have 3 or more nitro groups, and wherein the dinitrogroup is a precursor compound of the “diamino compound”. The dinitrocompound is conventionally converted to the diamino compound byreduction methods known in the art.

With respect to straight chain or branched alkyl, alkylene, alkoxy,alkylcarbonyloxy, acryloyloxyalkoxy, acryloyloxyalkyl,acryloyloxyalkene, alkyloxycarbonyloxy, alkylacryloyloxy,methacryloyloxyalkoxy, methacryloyloxyalkyl, methacryloyloxyalkene,alkylmethacryloyloxy, alkylmethacryloyloxy, alkylvinyl, alkylvinyloxy,alkylallyloxy and alkylene groups it is repeatedly pointed out that someor several of the —CH₂— groups may be replaced e.g. by heteroatoms, butalso by other groups, preferably bridging groups. In such cases it isgenerally preferred that such replacement groups are not directly linkedto each other. It is alternatively preferred that heteroatoms, and inparticular oxygen atoms are not directly linked to each other.

Preferably, A is unsubstituted or substituted phenanthrylene,naphthylene, biphenylene or phenylene, wherein the preferredsubstituent(s) is (are) a halogen atom, a hydroxy group and/or by apolar group, wherein the polar group is preferably nitro, cyano,carboxy; and/or by acryloyloxy, alkylacryl, alkylmethacryl,alkyl(en)acryl, alkyl(en)methacryl, acrylenacryl, methacrylenalkyl,methacryloyloxy, vinyl, vinyloxy, allyl, allyloxy, and/or by a cyclic,straight-chain or branched alkyl, which is unsubstituted, mono- orpoly-substituted by fluorine and/or chlorine, having from 1 to 20 carbonatoms, wherein one or more, preferably non-adjacent, —CH₂— groups mayindependently be replaced by a linking group and or an aromatic or analicyclic group, preferably the linking group is selected from —O—,—CO—, —CO—O—, —O—CO—.

More preferably A is substituted or unsubstituted naphthylene,biphenylene or phenylene, wherein the preferred substituent(s) is (are)halogen atom, hydroxy group and/or by acryloyloxy, alkylacryl,alkylmethacryl, acrylenacryl, methacrylenalkyl, methacryloyloxy,straight-chain or branched alkyl, alkoxy, alkylcarbonyloxy, and/oralkyloxycarbonyl groups, wherein the alkyl residue has from 1 to 20carbon atoms.

Most preferably A is substituted or unsubstituted phenylene, preferably1,4-phenylen, wherein the preferred substituent(s) is (are) a halogenatom, and/or by acryloyloxy or methacryloyloxy, and/or by an alkoxy,alkylacryl, alkylmethacryl, acrylenacryl, methacrylenalkyl,alkylcarbonyloxy, and/or alkyloxycarbonyl groups, wherein the alkylresidue has from 1 to 10 carbon atoms.

A preferred embodiment of the present invention concerns a diaminecompound of formula (I) as described above, wherein the followingcompound residue (Ia)

represents a straight-chain or branched C₁-C₁₆fluoralkyl group withterminal units selected from —CF₂H and —CF₃, preferably selected from—CF₂H or —CF₃, —CF₂CF₃, —CF₂CHF₂, —(CF₂)₂CF₃, —(CF₂)₂CHF₂, —(CF₂)₃CHF₂,—(CF₂)₃CF₃, —CF(CF₃)₂ and —CF₂(CHF)CF₃.

Preferably B is a straight-chain or branched C₁-C₁₂alkyl, wherein one ormore, preferably non-adjacent, —CH₂— group(s) may independently fromeach other be replaced by a group selected from

—O—, —CO, —CO—O—, —O—CO—, —NR¹—, —NR¹—CO—, —CO—NR¹—, —NR¹—CO—O—,—O—CO—NR¹—, —NR¹—CO—NR¹—, —CH═CH—, —C≡C—, —O—CO—O—, and—Si(CH₃)₂—O—Si(CH₃)₂—, an aromatic and an alicyclic group; and wherein:R¹ represents a hydrogen atom or C₁-C₆alkyl;with the proviso that oxygen atoms are not directly linked to eachother.

More preferably, B is a straight-chain or branched C₁-C₁₂alkyl, whereinone or more, preferably non-adjacent, —CH₂— group(s) may be replaced bya group selected from from —O—, —CO, —CO—O—, —O—CO—, —NR¹—, —NR¹—CO—,—CO—NR¹— or —CH═CH— wherein:

R¹ represents a hydrogen atom or C₁-C₆alkyl;with the proviso that oxygen atoms are not directly linked to eachother.

Most preferably, B is a straight-chain or branched C₁-C₈alkyl, whereinone or more, preferably non-adjacent, —CH₂— group(s) may be replaced bya group selected from from —O—, —CO, —CO—O—, —O—CO—, —NR¹—, —NR¹—CO—,—CO—NR¹— or —CH═CH— wherein:

R¹ represents a hydrogen atom or C₁-C₆alkyl;with the proviso that oxygen atoms are not directly linked to eachother.

Especially most preferably, B is a straight-chain or branchedC₁-C₈alkyl, wherein one or more, preferably non-adjacent, the —CH₂—group may be replaced by a group selected from —O—, —CO—, —CO—O—,—O—CO—, and —CH═CH—, with the proviso that oxygen atoms are not directlylinked to each other.

Preferably the compound residue (Ia) is:

trifluoromethyl; 2,2,2-trifluoroethyl; difluoromethyl; pentafluoroethyl;2,2-tetrafluoroethyl; 3,2-tetrafluoroethyl; 3,3,3-trifluoropropyl;2,2,3,3-tetrafluoropropyl; 2,2,3,3,3-pentafluoropropyl;hexafluoropropyl; heptafluoropropyl; 4,4,4-trifluorobutyl;tetrafluorobutyl; 3,3,4,4,4-pentafluorobutyl; hexafluorobutyl;2,2,3,3,4,4,4-heptafluorobutyl; 5,5,5-trifluoropentyl;tetrafluoropentyl; 4,4,5,5,5-pentafluoropentyl; hexafluoropentyl;3,3,4,4,5,5,5-heptafluoropentyl; 6,6,6-trifluorohexyl; tetrafluorohexyl;5,5,6,6,6-pentafluorohexyl; hexafluorohexyl;4,4,5,5,6,6,6-heptafluorohexyl; nonafluorohexyl;1-trifluoro-1,2,2,2-tertafluoroethoxy,2-trifluoro-2,3,3,3-tertafluoropropoxy,3-trifluoro-3,4,4,4-tertafluorobutoxy,4-trifluoro-4,5,5,5-tertafluoropentoxy,5-trifluoro-5,6,6,6-tertafluorohexoxy,6-trifluoro-6,7,7,7-tertafluoroheptoxy,7-trifluoro-7,8,8,8-tertafluorononoxy;fluoroalkoxy derivatives, such astrifluoromethoxy; 2,2,2-trifluoroethoxy; difluoromethoxy;pentafluoroethoxy; 1,1,2,2-tetrafluoroethoxy; 2,2,2,1-tetrafluoroethoxy;3,3,3-trifluoropropoxy; 2,2,3,3-tetrafluoropropoxy;2,2,3,3,3-pentafluoropropoxy; hexafluoropropoxyl; heptafluoropropoxy;4,4,4-trifluorobutoxy; tetrafluorobutoxy; 3,3,4,4,4-pentafluorobutoxy;2,2,3,3,4,4-hexafluorobutoxy; 2,2,3,3,4,4,4-heptafluorobutoxy;5,5,5-trifluoropentoxy; tetrafluoropentoxy;4,4,5,5,5-pentafluoropentoxy; hexafluoropentoxy;3,3,4,4,5,5,5-heptafluoropentoxy; 6,6,6-trifluorohexoxy;tetrafluorohexoxy; 5,5,6,6,6-pentafluorohexoxy; hexafluorohexoxy;4,4,5,5,6,6,6-heptafluorohexoxy; nonafluorohexoxy;trifluoromethylen carbamate; 2,2,2-trifluoroethylen carbamate;difluoromethylen carbamate; pentafluoroethylen carbamate;2,2-tetrafluorethylen carbamate; 3,2-tetrafluorethylen carbamate;3,3,3-trifluoropropylen carbamate; 2,2,3,3-tetrafluoropropylencarbamate; 2,2,3,3,3-pentafluoropropylen carbamate; hexafluoropropylencarbamate; heptafluoropropylen carbamate; 4,4,4-trifluorobutylencarbamate; tetrafluorobutylen carbamate; 3,3,4,4,4-pentafluorobutylencarbamate; hexafluorobutylen carbamate; 2,2,3,3,4,4,4-heptafluorobutylencarbamate; 5,5,5-trifluoropentylen carbamate; tetrafluoropentylencarbamate; 4,4,5,5,5-pentafluoropentylen carbamate; hexafluoropentylencarbamate; 3,3,4,4,5,5,5-heptafluoropentylen carbamate;6,6,6-trifluorohexylen carbamate; tetrafluorohexylen carbamate;5,5,6,6,6-pentafluorohexylen carbamate; hexafluorohexylen carbamate;4,4,5,5,6,6,6-heptafluorohexylen carbamate; nonafluorohexylen carbamate;fluoroalkyloyloxy derivatives, such astrifluoromethyloyloxy; 2,2,2-trifluoroethyloyloxy;pentafluoroethyloyloxy; 1,1,2,2-tetrafluorethyloyloxy;2,2,2,1-tetrafluorethyloyloxy; 3,3,3-trifluoropropyloyloxy;tetrafluoropropyloyloxy; 2,2,3,3,3-pentafluoropropyloyloxy;hexafluoropropyloyloxy; 1,1,2,2,3,3,3-heptafluoropropyloyloxy;4,4,4-trifluorobutyloyloxy; tetrafluorobutyloyloxy;3,3,4,4,4-pentafluorobutyloyloxy; hexafluorobutyloyloxy;2,2,3,3,4,4,4-heptafluorobutyloyloxy; 5,5,5-trifluoropentyloyloxy;tetrafluoropentyloyloxy; 4,4,5,5,5-pentafluoropentyloyloxy;hexafluoropentyloyloxy; 3,3,4,4,5,5,5-heptafluoropentyloyloxy;6,6,6-trifluorohexyloyloxy; tetrafluorohexyloyloxy;5,5,6,6,6-pentafluorohexyloyloxy; hexafluorohexyloyloxy;4,4,5,5,6,6,6-heptafluorohexyloyloxy;trifluoroacetyl; nonafluorohexyloyloxy;4,4,4-trifluorobut-2-enyl; 5,5,5-trifluoropent-1-enyl;6,6,6-trifluorohex-1-enyl; 7,7,7-trifluorohept-1-enyl;trifluoroacetylaminomethoxy; trifluoroacetylaminoethoxy;trifluoroacetylaminopropoxy; trifluoroacetylaminobutoxy; 2-fluoroethyl;3-fluoropropyl; 4-fluorobutyl; 5-fluoropentyl; 6-fluorohexyl;2-fluoroethoxy; 3-fluoropropoxy; 4-fluorobutoxy; 5-fluoropentoxy;6-fluorohexyloxy; 4-fluorobut-1-enyl; 5-fluoropent-1-enyl;6-fluorohex-1-enyl; 7-fluorohept-1-enyl;4,4,4-trifluoro-3-(trifluoromethyl)butoxy; 4,5,5-trifluoropent-4-enoxy;4,5,5-trifluoropent-4-enoyloxy; 5,6,6-trifluorohex-5-enoxy or5,6,6-trifluoropent-5-enoyloxy.

Especially preferred are fluoroalkoxy, preferably trifluor- andpentafluoro fluoroalkoxy derivatives, especially preferred are5,5,5-trifluoropentoxy and 4,4,5,5,5-pentafluoropentoxy.

D is preferably selected from formula (III):

H(R⁵)N-(Sp¹)_(k1)-(X¹)_(t1)-(Z³-C³)_(a3)-(Z⁴-C⁴)_(a4)—(X²)_(t2)-(Sp²)_(k2)-N(R⁶)H  (III)

wherein:

-   R⁵, R⁶ each independently from each other represents a hydrogen atom    or C₁-C₆alkyl;-   Sp¹, Sp² each independently from each other represent an    unsubstituted or substituted straight-chain or branched    C₁-C₂₀alkylene, in which one or more —CH₂-group may independently    from each other be replaced by a linking group, and-   k¹, k² each independently is an integer having a value of 0 or 1;    and-   X¹, X² each independently represents a linking spacer, preferably    selected from —O—, —S—, —NH—, N(CH₃)—, —CH(OH)—, —CO—, —CH₂(CO)—,    —SO—, —CH₂(SO)—, —SO₂—, —CH₂(SO₂)—, —COO—, —OCO—, —OCO—O—, —S—CO—,    —CO—S—, —SOO—, —OSO—, —SOS—, —CH₂—CH₂—, —OCH₂—, —CH₂O—, —CH═CH—, or    —C≡C— or a single bond; and-   t¹, t² each independently is an integer having a value of 0 or 1;    and-   C³, C⁴ each independently represents a non-aromatic, aromatic,    substituted or unsubstituted carbocyclic or heterocyclic group,    which may have a side chain T, and-   Z³ represents a bridging group; and-   Z⁴ represents a substituted or unsubstituted straight-chain or    branched C₁-C₂₀alkylene group, in which one or more —CH₂— group may    independently from each other be replaced by a non-aromatic,    aromatic, unsubstituted or substituted carbocyclic or heterocyclic    group; and/or a heteroatom and/or by a bridging group as described    above; preferably, Z⁴ has one of the meanings of Z³ or represents an    unsubstituted or substituted straight-chain or branched    C₁-C₁₄alkylene group, in which one or more, preferably non-adjacent,    —CH₂— group may be replaced by an oxygen atom and/or one or more    carbon-carbon single bond is replaced by a carbon-carbon double or a    carbon-carbon triple bond; and-   a₃, a₄ are independently integers from 0 to 3, such that a₃+a₄≦4;    and wherein-   D is at least once linked to at least one group S¹ in formula (I)    via group Sp¹ and/or Sp²; and/or linked via at least one    non-aromatic, aromatic, substituted or unsubstituted carbocyclic or    heterocyclic group of C³ and/or of group C⁴, and/or linked via at    least one side chain T of group C⁴ and/or of group C³; and/or linked    via group Z⁴; and at least one of k¹, k², a³ and a⁴ is not equal to    zero; and wherein    linking group and bridging group are as described above,-   and preferably compound of formula (I), wherein preferably, if n>1,    then the side chains [i.e. structures (I) without the group D] can    either be linked to the group D at one atomic position within group    D, e.g. two or three side chains connected to one single carbon atom    within group D, or they can be linked to group D at different atomic    positions within group D, e.g. at adjacent atomic positions within    group D, but also spaced further apart.

The term “side chain”, T, represents a substituted or unsubstitutedstraight-chain or branched C₁-C₂₀alkylene group(s), in which one or more—CH₂— group may independently from each other be replaced by anon-aromatic, aromatic, unsubstituted or substituted carbocyclic orheterocyclic group, or a heteroatom and/or by a bridging group, which isat least once linked to at least one group S¹ in formula (I).

Preferably D is selected from formula (III), wherein:

C³, C⁴ independently from each other are selected from a compound ofgroup G², wherein group G² denotes:

wherein

-   “-” denotes the connecting bonds of C³ and C⁴ to the adjacent groups    of compound of formula (III) as described above; and-   L is —CH₃, —COCH₃, —OCH₃, nitro, cyano, halogen, CH₂═CH—,    CH₂═C(CH₃)—, CH₂═CH—(CO)O—, CH₂═CH—O—, —NR⁵R⁶, CH₂═C(CH₃)—(CO)O—,    CH₂═C(CH₃)—O—,    wherein:    -   R⁵, R⁶ each independently from each other represents a hydrogen        atom or C₁-C₆alkyl;-   T represents a substituted or unsubstituted straight-chain or    branched C₁-C₂₀alkylene group, in which one or more —CH₂— group may    independently from each other be replaced by a non-aromatic,    aromatic, unsubstituted or substituted carbocyclic or heterocyclic    group, or a heteroatom and/or by a bridging group;-   m is an integer from 0 to 2; preferably 1 or 0; and more preferably    0;-   u₁ is an integer from 0 to 4, with the proviso that m+u₁ is ≦4; and-   u₂ is an integer from 0 to 3; with the proviso that m+u₂ is ≦3; and-   u₃ is an integer from 0 to 2; with the proviso that m+u₃ is ≦2.    D is more preferably selected from the following group of    structures: substituted or unsubstituted o-phenylenediamine,    p-phenylenediamine, m-phenylenediamine, biphenyldiamine,    aminophenylen-Z⁴-phenylenamino, wherein Z⁴ has the same meaning and    preferences as given above; naphthylenediamine, benzidine,    diaminofluorene, 3,4-diaminobenzoic acid, 3,4-diaminobenzyl alcohol    dihydrochloride, 2,4-diaminobenzoic acid,    L-(+)-threo-2-amino-1-(4-aminophenyl)-1,3-propanediol,    p-aminobenzoic acid, [3, 5-3h]-4-amino-2-methoxybenzoic acid,    L-(+)-threo-2-(N,N-dimethylamino)-1-(4-aminophenyl)-1,3-propanediol,    2,7-diaminofluorene, 4,4′-diaminooctafluorobiphenyl,    3,3′-diaminobenzidine, 2,7-diamino-9-fluorenone,    3,5,3′,5′-tetrabromo-biphenyl-4,4′-diamine,    2,2′-dichloro[1,1′-biphenyl]-4,4′-diamine,    3,9-diamino-1,11-dimethyl-5,7-dihydro-dibenzo(a,c)cyclohepten-6-one,    dibenzo(1,2)dithiine-3,8-diamine, 3,3′-diaminobenzophenone,    3,3′-diaminodiphenylmethane,    4,4-bis-(3-amino-4-hydroxyphenyl)-valeric acid,    2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane,    2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, tetrabromo    methylenedianiline, 2,7-diamino-9-fluorenone,    2,2-bis(3-aminophenyl)hexafluoropropane,    bis-(3-amino-4-chloro-phenyl)-methanone,    bis-(3-amino-4-dimethylamino-phenyl)-methanone,    3-[3-amino-5-(trifluoromethyl)benzyl]-5-(trifluoromethyl)aniline,    1,5-diaminonaphthalene, benzidine-3,3′-dicarboxylic acid,    4,4′-diamino-1,1′-binaphthyl, 4,4′-diaminodiphenyl-3,3′-diglycolic    acid, dihydroethidium, o-dianisidine,    2,2′-dichloro-5,5′-dimethoxybenzidine, 3-methoxybenzidine,    3,3′-dichlorobenzidine (diphenyl-d6),    2,2′-bis(trifluoromethyl)benzidine,    3,3′-bis(trifluoromethyl)benzidine, 3,3′-dichlorobenzidine-d6,    tetramethylbenzidine, di-(aminophenyl)alkylen and    -   from amino compounds listed below, which do not carry two amino        groups and are taken as derivatives with at least one additional        amino group: aniline, 4-amino-2,3,5,6-tetrafluorobenzoic acid,        4-amino-3,5-diiodobenzoic acid, 4-amino-3-methylbenzoic acid,        4-amino-2-chlorobenzoic acid, 4-aminosalicylic acid,        4-aminobenzoic acid, 4-aminophthalic acid,        1-(4-aminophenyl)ethanol, 4-aminobenzyl alcohol,        4-amino-3-methoxybenzoic acid, 4-aminophenyl ethyl carbinol,        4-amino-3-nitrobenzoic acid, 4-amino-3,5-dinitrobenzoic acid,        4-amino-3,5-dichlorobenzoic acid, 4-amino-3-hydroxybenzoic acid,        4-aminobenzyl alcohol hydrochloride, 4-aminobenzoic acid        hydrochloride, pararosaniline base,        4-amino-5-chloro-2-methoxybenzoic acid,        4-(hexafluoro-2-hydroxyisopropyl)aniline, piperazine-p-amino        benzoate, 4-amino-3,5-dibromobenzoic acid, isonicotinic acid        hydrazide p-amino-salicylate salt, 4-amino-3,5-diiodosalicylic        acid, 4-amino-2-methoxybenzoic acid,        2-[2-(4-aminophenyl)-2-hydroxy-1-(hydroxymethyl)ethyl]isoindoline-1,3-dione,        4-amino-2-nitrobenzoic acid, ethyl        2-(4-aminophenyl)-3,3,3-trifluoro-2-hydroxypropanoate, ethyl        2-(4-amino-3-methylphenyl)-3,3,3-trifluoro-2-hydroxypropanoate,        ethyl        2-(4-amino-3-methoxyphenyl)-3,3,3-trifluoro-2-hydroxypropanoate,        4-aminonaphthalene-1,8-dicarboxylic acid,        4-amino-3-chloro-5-methylbenzoic acid,        4-amino-2,6-dimethylbenzoic acid, 4-amino-3-fluorobenzoic acid,        4-amino-5-bromo-2-methoxybenzenecarboxylic acid,        3,3′-tolidine-5-sulfonic acid,    -   or their derivatives, again with the proviso that compounds        listed which do not carry two amino groups are taken as        derivatives with at least one additional amino group.

The diamine groups D are commercial available or accessible by knownmethods. The second amino group is accessible for example bysubstitution reaction.

D is further more preferably selected from the group of the followingcompounds:

wherein

-   L, L₁, L₂ and L₃ are indepentyl from each other —CH₃, —COCH₃, —OCH₃,    nitro, cyano, halogen, CH₂═CH—, CH₂═C(CH₃)—, CH₂═CH—(CO)O—,    CH₂═CH—O—, —NR⁵R⁶, CH₂═C(CH₃)—(CO)O— or CH₂═C(CH₃)—O—,-   T, T₁, T₂ and T₃ are indepentyl from each other a substituted or    unsubstituted straight-chain or branched C₁-C₂₀alkylene group, in    which one or more —CH₂— group(s) may independently from each other    be replaced by a non-aromatic, aromatic, unsubstituted or    substituted carbocyclic or heterocyclic group, and/or a heteroatom    and/or by a bridging group;-   “-” is a single bond,-   q is an integer of 1 or 2; and-   q1, q2 and q3 are indepentyl from each other an integer from 0 to 2;    preferably 1 or 2;-   m is an integer of 1 or 2;-   m1, m2 and m3 are indepentyl from each other an integer from 0 to 2;    preferably 1 or 2;-   u₃, u₃′ and u₃″ are indepentyl from each other an integer from 0 to    2;-   R⁵, R⁶ and Z⁴ are as described above; and wherein-   D is at least once linked to at least one group S¹ in formula (I)    via a single bond “-”; or via a side chain T, T₁, T₂ or T₃; or via    group Z⁴;    with the proviso that    u3+q, or u3+m is ≦4;    u3+q1 and/or u3′+q2 or/and u3+m1, or/and u3′+m2, or/and u3″+q3,    or/and u3″+m3 is ≦4;    q1+q2, and m1+m2; and q1+q2+q3, and m1+m2+m3 is ≧1.

Most preferred are diamine compounds according to the invention, whereinD is a selected from the group of the following compounds:

“-” denotes the linking(s) of D to S¹ in compound (I) and represents asingle bond; andL is —CH₃, —COCH₃, —OCH₃, nitro, cyano, halogen, CH₂═CH—, CH₂═C(CH₃)—,CH₂═CH—(CO)O—, CH₂═CH—O—, —NR⁵R⁶, CH₂═C(CH₃)—(CO)O— or CH₂═C(CH₃)—O—,wherein:

-   R⁵, R⁶ each independently from each other represents a hydrogen atom    or C₁-C₆alkyl;-   u₃ is an integer from 0 to 2.

E preferably represents an phenylene, an oxygen atom or a —N(H)— group,more preferred E is oxygen or a —N(H)— group, and most preferred E isoxygen.

-   Preferably, S¹, S² each independently from each other represents a    single bond or a spacer unit, which is a cyclic, straight-chain or    branched, substituted or unsubstituted C₁-C₂₄alkylen, in which one    or more, preferably non-adjacent, —CH₂— group may be replaced by a    linking group, and/or a non-aromatic, aromatic, unsubstituted or    substituted carbocyclic or heterocyclic group of formula (IV):

-(Z¹-C¹)_(a1)-(Z²-C²)_(a2)-(Z^(1a))_(a3)-  (IV)

wherein:

-   C¹, C² each independently represents a non-aromatic, aromatic,    optionally substituted carbocyclic or heterocyclic group, preferably    connected to each other via the bridging groups Z¹ and Z² and/or    Z^(1a), preferably C¹ and C² are connected at the opposite positions    via the bridging groups Z¹ and Z² and/or Z^(1a), so that groups S¹    and/or S² have a long molecular axis, and-   Z¹, Z², Z^(1a) each independently represents a bridging group,    preferably selected from —CH(OH)—, —CH₂—, —O—, —CO—, —CH₂(CO)—,    —SO—, —CH₂(SO)—, —SO₂—, —CH₂(SO₂)—, —COO—, —OCO—, —COCF₂—, —CF₂CO—,    —S—CO—, —CO—S—, —SOO—, —OSO—, —SOS—, —CH₂—CH₂—, —OCH₂—, —CH₂O—,    —CH═CH—, —C≡C—, —CH═CH—COO—, —OCO—CH═CH—, —CH═N—, —C(CH₃)═N—,    —O—CO—O—, —N═N— or a single bond; and-   a₁, a₂, a₃ each independently represents an integer from 0 to 3,    such that a₁+a₂+a₃≦6, wherein preferably S² is linked to A via Z¹;    preferably a₃ is 0 and a₁+a₂≦4.

More preferred S¹ represents a straight-chain or branched C₁-C₂₄alkylen,wherein one or more —CH₂— group may independently be replaced by alinking group or/and a group represented by the formula (IV), wherein:

-   C¹, C² are selected from a compound of group G¹, wherein group G¹    is:

wherein:

-   “-” denotes the connecting bonds of C¹ and C² to the adjacent groups    in formula (IV); and-   L is —CH₃, —OCH₃, —COCH₃, nitro, cyano, halogen, CH₂═CH—,    CH₂═C(CH₃)—, CH₂═CH—(CO)O—, CH₂═CH—O—, CH₂═C(CH₃)—(CO)O—, or    CH₂═C(CH₃)—O—,-   u₁ is an integer from 0 to 4; and-   u₂ is an integer from 0 to 3; and-   u₃ is an integer from 0 to 2; and-   Z¹, Z², Z^(1a) each independently represents —O—, —CO—, —COO—,    —OCO—, —COCF₂—, —CF₂CO—, —CH₂—CH₂—, —OCH₂—, —CH₂O—, —CH═CH—, —C≡C—,    —CH═CH—COO—, —OCO—CH═CH— or a single bond; with the proviso that    heteroatoms are not directly linked to each other, and-   a₁, a₂, a₃ each independently represents an integer from 0 to 3,    such that a₁+a₂+a₃≦6; preferably a₃ is 0 and a¹+a²≦4.

Most preferred S¹ represents a single bond or a spacer unit such as astraight-chain or branched C₁-C₁₄alkylen, wherein one or more,preferably non adjactent, —CH₂— group may independently be replaced by alinking group and/or a group represented by formula (IV), wherein:

-   C¹, C² each independently represents a 1,4-phenylene,    2-methoxy-1,4-phenylene, 1,4-cyclohexylene or a 4,4′-biphenylene    group; and-   Z¹, Z², Z^(1a) each independently represents —COO—, —OCO—,    —CH₂—CH₂—, —OCH₂—, —CH₂O—, —CH═CH—, —C≡C—, —CH—CH—COO—, —OCO—CH═CH—    or a single bond; and-   a₁, a₂, a₃ are independently 0 or 1, preferably a₃ is 0.

Especially most preferred S¹ represents a straight-chain C₁-C₁₂alkylen,wherein one or more —CH₂— groups may be replaced by —O—, —O(CO)—,—(CO)O—, —NR₁CO—, —CONR₁—, wherein R₁ is hydrogen or C₁-C₆alkyl or agroup of formula (IV), wherein:

-   C¹, C² each independently represents 1,4-phenylene; and-   Z¹, Z², Z^(1a) each independently represents —COO—, —OCO—,    —CH₂—CH₂—, —OCH₂—, —CH₂O—, —CH═CH—, —C≡C—, —CH═CH—COO—, —OCO—CH═CH—,    or a single bond; and-   a₁, a₂, a₃ are independently 0 or 1, preferably a₃ is 0.

More preferred S² represents a spacer unit such as a straight-chain orbranched C₁-C₂₄alkylen, wherein one or more —CH₂— groups isindependently replaced by a group represented by the formula (IV),wherein:

-   C¹, C² are selected from group G¹, with the above given meaning; and-   Z¹, Z², Z^(1a) each independently represents —O—, —CO—, —COO—,    —OCO—, —COCF₂—, —CF₂CO—, —CH₂—CH₂—, —OCH₂—, —CH₂O—, —CH═CH—, —C≡C—,    —CH═CH—COO—, —OCO—CH═CH— or a single bond; with the proviso that    heteroatoms are not directly linked to each other, and-   a₁, a₂, a₃ are each independently represents an integer from 0 to 3,    such that a₁+a₂+a₃≦6, and preferably a₁+a₂≦4 and a₃ is 0; and    wherein preferably S² is linked to A via Z¹.

Most preferred S² represents a straight-chain or branched

C₁-C₁₂alkylen, wherein one or more —CH₂— group is independently bereplaced by a group represented by the formula (IV), and more mostpreferred S² represents a group of formula (IV), wherein

-   C¹, C² each independently represents a 1,4-phenylene which is    unsubstituted or mono or poly-substituted by a halogen atom, and/or    by an alkoxy, alkylcarbonyloxy or an alkyloxycarbonyl group, having    form 1 to 10 carbon atoms, 1,4-cyclohexylene or a 4,4′-biphenylene    group; and-   Z¹, Z², Z^(1a) each independently represents —COO—, —OCO—,    —CH₂—CH₂—, —OCH₂—, —CH₂O—, —CH═CH—, —C≡C—, —CH═CH—COO—, —OCO—CH═CH—    or a single bond; and-   a₁, a₂, a₃ are independently 0 or 1, wherein preferably S² is linked    to A via Z¹.

Especially most preferred S² represents a group of formula (IVa)

(Z¹-C¹)_(a) ₁ -(Z^(1a))_(a) ₃ -  (IVa)

wherein:

-   C¹ represents a non-aromatic, aromatic, unsubstituted or substituted    carbocyclic or heterocyclic group, preferably selected from a    compound of group G1, and-   Z¹, Z^(1a) each independently from each other represent —COO—,    —OCO—, —OCO(C₁-C₆)alkyl, —COOCH₂(C₁-C₆)alkyl-, —CH₂—CH₂—, —OCH₂—,    —CH₂O—, —CH═CH—, —C≡C—, —CH═CH—COO—, —OCO—CH═CH—, or a single bond,    or a straight-chain or branched, substituted or unsubstituted    C₁-C₈alkylen, wherein one or more —CH₂— group may independently from    each other be replaced by a linking group, preferably by —O—, as    described above;    a₁, a₃ represents independently from each other 1, wherein    preferably S² is linked to A via Z¹.

Further, especially most preferred S² represents a group of formula(IVa)

-(Z¹-C¹)_(a) ₁ -(Z^(1a))_(a) ₃ -  (IVa)

wherein:

-   C¹ represents a 1,4-phenylene which is unsubstituted or mono or    poly-substituted by a halogen atom, and/or by an alkoxy,    alkylcarbonyloxy or an alkyloxycarbonyl group, having form 1 to 10    carbon atoms,-   Z¹, Z^(1a) each independently from each other represent —COO—,    —OCO—, —CH₂—CH₂—, —OCH₂—, —CH₂O—, —CH═CH—, —C≡C—, —CH═CH—COO—,    —OCO—CH═CH—, or a single bond, or a straight-chain or branched,    substituted or unsubstituted C₁-C₈alkylen, wherein one or more —CH₂—    group may independently from each other be replaced by a linking    group as described above, preferably by —O—, —COO—, —OCO—,-   a₁, a₃ represents independently from each other 1, wherein    preferably S² is linked to A via Z¹.-   Another preferred embodiment of the present invention relates to a    diamine compound (I), referring to any of the preceding definitions    comprising these diamine compounds, wherein A represents    phenanthrylene, biphenylene, naphthylene, or phenylene, which is    unsubstituted or mono- or poly-substituted by a halogen atom,    hydroxy group and/or by a polar group, preferably nitro, cyano,    carboxy; and/or by acryloyloxy, methacryloyloxy, vinyl, vinyloxy,    allyl, allyloxy, and/or by a cyclic, straight-chain or branched    C₁-C₁₂alkyl residue, which is unsubstituted, mono- or    poly-substituted by fluorine and/or chlorine, wherein one or more    —CH₂— group may independently be replaced by a linking group and or    an aromatic or an alicyclic group,    and    wherein the compound residue (Ia) of compound of formula (I) as    described above

represents a straight-chain or branched C₁-C₁₂fluoralkyl group, wherein

-   F is fluorine, and-   x₁ is an integer from 1 to 10,-   B represents a straight-chain or branched C₁-C₁₂alkyl group, which    is unsubstituted or in addition to its fluorine substituent(s)    substituted by di-(C₁-C₁₆alkyl)amino, C₁-C₆alkyloxy, nitro, cyano    and/or chlorine; and wherein one or more —CH₂— group may    independently from each other be replaced by a linking group    selected from —O—, —CO—, —CO—O—, —O—CO—, —NR¹—, —NR¹—CO—, —CO—NR¹—    and —CH═CH—, wherein:    -   R¹ represents a hydrogen atom or C₁-C₆alkyl;    -   with the proviso that oxygen atoms are not directly linked to        each other;    -   and    -   wherein the C₁-C₁₂fluoralkyl group has terminal units selected        from —CF₂H and —CF₃, preferably selected from    -   —CF₂H or —CF₃, —CF₂CF₃, —CF₂CHF₂, —(CF₂)₂CF₃, —(CF₂)₂CHF₂,        —(CF₂)₃CHF₂, —(CF₂)₃CF₃, —CF(CF₃)₂ and —CF₂(CHF)CF₃,-   D represents an optionally substituted aliphatic, aromatic or    alicyclic diamine group having from 1 to 40 carbon atoms selected    from formula (III),

HN(R⁵)-(Sp¹)_(k1)-(X¹)_(t1)-(Z³-C³)_(a3)-(Z⁴-C⁴)_(a4)—(X²)_(t2)-(Sp²)_(k2)-N(R⁶)H  (III)

wherein

-   -   k¹, k² are 0 or 1, and    -   t¹, t² are 0, and    -   R⁵, R⁶ are identical and represent a hydrogen atom, a methyl, an        ethyl or an isopropyl group; and    -   C³, C⁴ independently from each other are selected from compound        of a group G² as described above;    -   Z³ represents a group selected from —CH(OH)—, —CH(CH₃)—,        —C(CH₃)₂—, —CO—, —COO—, —OCO—, —COCF₂—, —CF₂CO— or a single        bond; and    -   Z⁴ has one of the meanings of Z³ or represents a substituted or        unsubstituted straight-chain or branched C₁-C₂₀alkylene, in        which one or more, preferably non-adjacent, —CH₂— group may        independently from each other be replaced by cyclohexylen,        phenylen, aromatic or non-aromatic N-heterocycle; or by a        heteroatom and/or by an oxygen atom; and/or one or more        carbon-carbon single bond is replaced by a carbon-carbon double        or a carbon-carbon triple bond;    -   a³, a⁴ each independently represents an integer from 0 to 2 such        that a³+−a⁴≦3;    -   Sp¹, Sp², X¹, X² have the same meaning as described above;

-   E represents an phenylene, an oxygen atom or a —N(H)— group;

-   S¹ represents a single bond or a cyclic, straight-chain or branched,    substituted or unsubstituted C₁-C₂₄alkylen, wherein one or more    —CH₂— group may independently from each other be replaced by a    linking group as described above;

-   S² represents a non-aromatic, aromatic, unsubstituted or substituted    carbocyclic or heterocyclic group of formula (IV):

-(Z¹-C¹)_(a1)-(Z²-C²)_(a2)-(Z^(1a))_(a3)-  (IV)

-   -   wherein:    -   C¹, C² each independently represents a non-aromatic, aromatic,        unsubstituted or substituted carbocyclic or heterocyclic group,        and    -   Z¹, Z², Z^(1a) each independently represents a bridging group,        and    -   a¹, a², a³ each independently represents an integer from 0 to 3,        such that a¹+a²+a³≦6, preferably a¹+a²≦4 and a³ is 0;    -   wherein the bridging groups Z¹, Z^(1a) and Z² are as described        above,

-   X, Y are hydrogen atoms, and

-   n is 1, 2 or 3, and n1 is 1 or 2; preferably n1 is 1.    with the proviso that if n is 2 or 3 each A, B, x₁, D, E, S¹ and S²    may be identical or different, and if n1 is 2 each B, x1 may be    identical or different.

A more preferred embodiment of the present invention relates to diaminecompounds (I), referring to any of the preceding definitions, and toalignment materials comprising these diamine compounds wherein

-   A represents a biphenylene, naphthylene or phenylene group, which is    unsubstituted or mono- or poly-substituted by a halogen atom, a    hydroxy group, and/or by acryloyloxy, and/or methacryloyloxy groups,    and/or by straight-chain or branched alkyl, alkoxy,    alkylcarbonyloxy, and/or alkyloxycarbonyl groups having from 1 to 20    carbon atoms,    and    wherein the compound residue (Ia) of compound of formula (I) as    described in claim 1

represents a straight-chain or branched C₁-C₈fluoralkyl group, wherein

-   F is fluorine, and-   x₁ is an integer from 1 to 9,-   B represents a straight-chain or branched C₁-C₈alkyl group, which is    unsubstituted or in addition to its fluorine substituent(s)    substituted by di-(C₁-C₁₆alkyl)amino, C₁-C₆alkyloxy, nitro, cyano    and/or chlorine; and wherein one or more —CH₂— group may    independently from each other be replaced by a linking group    selected from —O—, —CO—, —CO—O—, —O—CO—, —NR¹—, —NR¹—CO—, —CO—NR¹—    and —CH═CH—, wherein:-   R¹ represents a hydrogen atom or C₁-C₈alkyl; with the proviso that    oxygen atoms are not directly linked to each other; and-   D represents an optionally substituted aliphatic, aromatic or    alicyclic diamine group having from 1 to 40 carbon atoms,    represented by formula (III) and is most preferably selected from    the following group of structures: substituted or unsubstituted    o-phenylenediamine, p-phenylenediamine, m-phenylenediamine,    aminophenylen-Z⁴-phenylenamino; or m-phenylenediamine with a    substituted or unsubstituted straight-chain or branched    C₁-C₂₀alkylene group, in which one or more —CH₂— group may    independently from each other be replaced by a non-aromatic,    aromatic, unsubstituted or substituted carbocyclic or heterocyclic    group, or a heteroatom and/or by a bridging group; wherein Z⁴ has    the above given meaning; benzidine, diaminofluorene,    3,4-diaminobenzoic acid, 3,4-diaminobenzyl alcohol dihydrochloride,    2,4-diaminobenzoic acid,    L-(+)-threo-2-amino-1-(4-aminophenyl)-1,3-propanediol,    p-aminobenzoic acid, [3, 5-3h]-4-amino-2-methoxybenzoic acid,    L-(+)-threo-2-(N,N-dimethylamino)-1-(4-aminophenyl)-1,3-propanediol,    2,7-diaminofluorene, 4,4′-diaminooctafluorobiphenyl,    3,3′-diaminobenzidine, 2,7-diamine-9-fluorenone,    3,5,3′,5′-tetrabromo-biphenyl-4,4′-diamine,    2,2′-dichloro[1,1′-biphenyl]-4,4′-diamine,    3,9-diamine-1,11-dimethyl-5,7-dihydro-dibenzo(a,c)cyclohepten-6-one,    dibenzo(1,2)dithiine-3,8-diamine, 3,3′-diaminobenzophenone,    3,3′-diaminediphenylmethane,    4,4-bis-(3-amino-4-hydroxyphenyl)-valeric acid,    2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane,    2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, tetrabromo    methylenedianiline, 2,7-diamine-9-fluorenone,    2,2-bis(3-aminophenyl)hexafluoropropane,    bis-(3-amino-4-chloro-phenyl)-methanone,    bis-(3-amino-4-dimethylamino-phenyl)-methanone,    3-[3-amino-5-(trifluoromethyl)benzyl]-5-(trifluoromethyl)aniline,    1,5-diaminonaphthalene, benzidine-3,3′-dicarboxylic acid,    4,4′-diamino-1,1′-binaphthyl, 4,4′-diaminediphenyl-3,3′-diglycolic    acid, dihydroethidium, o-dianisidine,    2,2′-dichloro-5,5′-dimethoxybenzidine, 3-methoxybenzidine,    3,3′-dichlorobenzidine (diphenyl-d6),    2,2′-bis(trifluoromethyl)benzidine,    3,3′-bis(trifluoromethyl)benzidine, 3,3′-dichlorobenzidine-d6,    tetramethylbenzidine, di-(aminophenyl)alkylen    and    -   from amino compounds listed below, which do not carry two amino        groups and are taken as derivatives with at least one additional        amino group: aniline, 4-amino-2,3,5,6-tetrafluorobenzoic acid,        4-amino-3,5-diiodobenzoic acid, 4-amino-3-methylbenzoic acid,        4-amino-2-chlorobenzoic acid, 4-aminosalicylic acid,        4-aminobenzoic acid, 4-aminophthalic acid,        1-(4-aminophenyl)ethanol, 4-aminobenzyl alcohol,        4-amino-3-methoxybenzoic acid, 4-aminophenyl ethyl carbinol,        4-amino-3-nitrobenzoic acid, 4-amino-3,5-dinitrobenzoic acid,        4-amino-3,5-dichlorobenzoic acid, 4-amino-3-hydroxybenzoic acid,        4-aminobenzyl alcohol hydrochloride, 4-aminobenzoic acid        hydrochloride, pararosaniline base,        4-amino-5-chloro-2-methoxybenzoic acid,        4-(hexafluoro-2-hydroxyisopropyl)aniline, piperazine-p-amino        benzoate, 4-amino-3,5-dibromobenzoic acid, isonicotinic acid        hydrazide p-amino-salicylate salt, 4-amino-3,5-diiodosalicylic        acid, 4-amino-2-methoxybenzoic acid,        2-[2-(4-aminophenyl)-2-hydroxy-1-(hydroxymethyl)ethyl]isoindoline-1,3-dione,        4-amino-2-nitrobenzoic acid, ethyl        2-(4-aminophenyl)-3,3,3-trifluoro-2-hydroxypropanoate, ethyl        2-(4-amino-3-methylphenyl)-3,3,3-trifluoro-2-hydroxypropanoate,        ethyl        2-(4-amino-3-methoxyphenyl)-3,3,3-trifluoro-2-hydroxypropanoate,        4-aminonaphthalene-1,8-dicarboxylic acid,        4-amino-3-chloro-5-methylbenzoic acid,        4-amino-2,6-dimethylbenzoic acid, 4-amino-3-fluorobenzoic acid,        4-amino-5-bromo-2-methoxybenzenecarboxylic acid,        3,3′-tolidine-5-sulfonic acid, or their derivatives, again with        the proviso that compounds listed which do not carry two amino        groups are taken as derivatives with at least one additional        amino group, and-   E represents an oxygen atom or a —N(H)— group;-   S¹ represents a spacer unit such a straight-chain or branched    C₁-C₁₄alkylene groups, wherein one or more —CH₂— groups may    independently be replaced by a group represented by formula (IV) as    defined above, wherein:-   C¹, C² each independently represents a 1,4-phenylene,    2-methoxy-1,4-phenylene, 1,4-cyclohexylene or a 4,4′-biphenylene    group; and-   Z¹, Z², Z^(1a) each independently represents —COO—, —OCO—,    —CH₂—CH₂—, —OCH₂—, —CH₂O—, —CH═CH—, —C≡C—, —CH═CH—COO—, —OCO—CH═CH—    or a single bond; and-   a¹, a², a³ are independently 0 or 1; preferably a³ is 0,-   S² represents a spacer unit of formula (IV) as defined above,    wherein preferably S² is linked to A via Z¹; and wherein    -   C¹, C² each independently represents a 1,4-phenylene which is        unsubstituted or mono or poly-substituted by a halogen atom,        and/or by an alkoxy, alkylcarbonyloxy or an alkyloxycarbonyl        group, having form 1 to 10 carbon atoms, 1,4-cyclohexylene or a        4,4′-biphenylene group; and-   Z¹, Z², Z^(1a) each independently represents —O—, —COO—, —OCO—,    —CH₂—CH₂—, —OCH₂—, —CH₂O—, —CH═CH—, —C≡C—, —CH═CH—COO—, —OCO—CH═CH—    or a single bond; and-   a¹, a², a³ are independently 0 or 1; preferably a³ is 0,-   n is 1 or 2, and n1 is 1, or 2, preferably 1;    with the proviso that if n is 2 or 3 each A, B, x₁, D, E, S¹, S², X,    Y may be identical or different; and if n1 is 2 each B, x₁ is    identical or different.

Another preferred embodiment of the present invention relates to adiamine compound represented by one of the general formula (I),referring to any of the preceding definitions, and preferably toalignment materials comprising this diamine compound wherein

-   A represents 1,4-phenylene, which is unsubstituted or mono- or    poly-substituted by a halogen atom, and/or by acryloyloxy or    methacryloyloxy, and/or by an alkoxy, alkylcarbonyloxy or an    alkyloxycarbonyl group, having from 1 to 10 carbon atoms,    and    wherein the compound residue (Ia) of compound of formula (I) as    described above

represents a straight-chain or branched C₁-C₈fluoralkyl group, wherein

-   F is fluorine, and-   x₁ is an integer from 1 to 9,-   B represents a straight-chain or branched C₁-C₈alkyl group, which is    unsubstituted or in addition to its fluorine substituent(s)    substituted by di-(C₁-C₁₆alkyl)amino, C₁-C₆alkyloxy, nitro, cyano    and/or chlorine; and wherein one or more —CH₂— group may    independently from each other be replaced by a linking group    selected from —O—, —CO—, —CO—O—, —O—CO—, —NR¹—, —NR¹—CO—, —CO—NR¹—    and —CH═CH—, wherein:    -   R¹ represents a hydrogen atom or C₁-C₆alkyl;    -   with the proviso that oxygen atoms are not directly linked to        each other; and    -   wherein the C₁-C₁₂fluoralkyl group has terminal units selected        from —CF₂H and —CF₃, preferably selected from    -   —CF₂H or —CF₃, —CF₂CF₃, —CF₂CHF₂, —(CF₂)₂CF₃, —(CF₂)₂CHF₂,        —(CF₂)₃CHF₂, —(CF₂)₃CF₃, —CF(CF₃)₂ and —CF₂(CHF)CF₃,-   D represents an unsubstituted o-phenylenediamine,    p-phenylenediamine, m-phenylenediamine, biphenyldiamine,    aminophenylen-Z⁴-phenylenamino, naphthylenediamine, or a    m-phenylenediamine with a substituted or unsubstituted    straight-chain or branched C₁-C₂₀alkylene group, in which one or    more —CH₂— group may independently from each other be replaced by a    non-aromatic, aromatic, unsubstituted or substituted carbocyclic or    heterocyclic group, or a heteroatom and/or by a bridging group;    -   wherein    -   Z⁴ is as defined above;-   E represents an oxygen atom;-   S¹ represents a single bond or a straight-chain C₁-C₈alkylene group,    wherein one —CH₂— group may be may be replaced by —O—, —OCO—, —COO—,    —NR₁CO—, —CONR₁—, wherein R₁ is hydrogen or C₁-C₆alkyl,-   S² is replaced by a group of formula (IVa) as described above,    wherein:    -   C¹ represents a 1,4-phenylene which is unsubstituted or mono or        poly-substituted by a halogen atom, and/or by an alkoxy,        alkylcarbonyloxy or an alkyloxycarbonyl group, having form 1 to        10 carbon atoms,    -   Z¹, Z^(1a) represents —O—, —COO—, —OCO—, —COO(C₁-C₆)alkylen,        —OCO(C₁-C₆)alkylen, —CH₂—CH₂—, —OCH₂—, —CH₂O—, —CH═CH—, —C≡C—,        —CH═CH—COO—, —OCO—CH═CH—, or a single bond;    -   X, Y are hydrogen atoms, and    -   n is 1 or 2, and n1 is 1 or 2 and preferably 1;-   with the proviso that if n or n1 is 2 each A, B, x₁, D, E, S¹ and S²    may be identical or different; and if n1 is 2 each B, x₁ is    identical or different.

Most preferred embodiment of the present invention relates to diaminecompounds represented by one of the general formula (I), referring toany of the preceding definitions, and to alignment materials comprisingthese diamine compounds wherein

-   S² is replaced by a group of formula (IV), wherein:-   C¹ represents 1,4-phenylene; and-   Z¹, Z^(1a) represent each independently from each other —COO—,    —OCO—, —CH₂—CH₂—, —OCH₂—, —CH₂O—, —CH═CH—, —C≡C—, —CH═CH—COO—,    —OCO—CH═CH—, or a single bond;-   a₁ represents 1, and a₃ represents 0-   S² is linked to A via Z¹.-   Especially most preferred embodiment of the present invention    relates to Diamine compounds of formulae (VI), (VII), (VIII), (IX),    (X), (XI), (XIa) and (XIb)

whereinA, B, x₁, n, n1, D, E, S², S¹, X and Y, R⁵, R⁶ and Z⁴ have the abovegiven meanings and preferences as given above; preferably n1 is 1;L is —CH₃—, —OCH₃, —COCH₃, nitro, cyano, halogen, CH₂═CH—, CH₂═C(CH₃)—,CH₂═CH—(CO)O—, CH₂═CH—O—, CH₂═C(CH₃)—(CO)O—, or CH₂═C(CH₃)—O—,u3 is an integer from 0 to 2.

Further, especially most preferred embodiment of the present inventionrelates to diamine compounds of formula (XII)

wherein x₁, n, n1, D, E, S¹, X, Y, Z¹, L, u₁ and u₂ have the above givenmeanings and preferences.

Preferred diamine compounds of formula (XII) are compounds, wherein Z¹is —COO—, —OCO—, —OCO(C₁-C₆)alkylen or —COO(C₁-C₆)alkylen, or a singlebond, or a straight-chain or branched, substituted or unsubstitutedC₁-C₈alkylen, wherein one or more —CH₂— group may independently fromeach other be replaced independently from each other by a linking group,preferably by —O—.

Further, especially most preferred diamine is compound of formula (XIIa)

wherein n, n1, D, E, S¹, Z¹, L, u₁ and u₂ X and Y have the above givenmeanings and preferences as above, andwherein the following compound residue

represents a straight-chain or branched C₁-C₈fluoralkyl group, wherein

-   F is fluorine, and-   x₁ is an integer from 1 to 9,-   B represents a straight-chain or branched C₁-C₈alkyl group, which is    unsubstituted or in addition to its fluorine substituent(s)    substituted by di-(C₁-C₁₆alkyl)amino, C₁-C₆alkyloxy, nitro, cyano    and/or chlorine; and wherein one or more —CH₂— group may    independently be replaced by a linking group selected from —O—,    —CO—, —CO—O—, —O—CO—, —NR¹—, —NR¹—CO—, —CO—NR¹— and —CH═CH—,    wherein:    -   R¹ represents a hydrogen atom or C₁-C₆alkyl;    -   with the proviso that oxygen atoms are not directly linked to        each other;    -   and    -   wherein the C₁-C₁₂fluoralkyl group has terminal units selected        from —CF₂H and —CF₃, preferably selected from    -   —CF₂H or —CF₃, —CF₂CF₃, —CF₂CHF₂, —(CF₂)₂CF₃, —(CF₂)₂CHF₂,        —(CF₂)₃CHF₂, —(CF₂)₃CF₃, —CF(CF₃)₂ and —CF₂(CHF)CF₃.

Most preferred diamine is

wherein S¹ has the above given meanings and preferences as above;especially most preferred S¹ represents a straight-chain C₁-C₁₂alkylen,wherein one or more —CH₂— group may be replaced by —O—, —O(CO)—,—(CO)O—, —NR₁CO—, —CONR₁—, wherein R₁ is hydrogen or C₁-C₆alkyl or agroup of formula (IV), wherein:

-   C¹, C² each independently represents 1,4-phenylene; and-   Z¹, Z², Z^(1a) each independently represents —COO—, —OCO—,    —CH₂—CH₂—, —OCH₂—, —CH₂O—, —CH═CH—, —C≡C—, —CH═CH—COO—, —OCO—CH═CH—,    or a single bond; and-   a₁, a₂, a₃ are independently 0 or 1, preferably a₃ is 0;    and    wherein the following compound residue

represents a straight-chain or branched C₁-C₈fluoralkyl group, wherein

-   F is fluorine, and-   x₁ is an integer from 1 to 9,-   B represents a straight-chain or branched C₁-C₈alkyl group, which is    unsubstituted or in addition to its fluorine substituent(s)    substituted by di-(C₁-C₁₆alkyl)amino, C₁-C₆alkyloxy, nitro, cyano    and/or chlorine; and wherein one or more —CH₂— group may    independently be replaced by a linking group selected from —O—,    —CO—, —CO—O—, —O—CO—, —NR¹—, —NR¹—CO—, —CO—NR¹— and —CH═CH—,    wherein:    -   R¹ represents a hydrogen atom or C₁-C₆alkyl;    -   with the proviso that oxygen atoms are not directly linked to        each other;    -   and    -   wherein the C₁-C₈fluoralkyl group has terminal units selected        from —CF₂H and —CF₃, preferably selected from    -   —CF₂H or —CF₃, —CF₂CF₃, —CF₂CHF₂, —(CF₂)₂CF₃, —(CF₂)₂CHF₂,        —(CF₂)₃CHF₂, —(CF₂)₃CF₃, —CF(CF₃)₂ and —CF₂(CHF)CF₃.

Another preferred embodiment of the present invention relates to diaminecompounds represented by the general formula (I), which may be used inthe subsequent manufacturing processes as such or in combination withone or more additional other diamines, preferably those of formula (L)as given below.

The diamine (L) represents an optionally substituted aliphatic, aromaticor alicyclic diamino group having from 1 to 40 carbon atoms andpreferably made from or selected from the following group of structures:aniline, p-phenylenediamine, m-phenylenediamine, benzidine,diaminofluorene, or their derivatives, with the proviso that compoundslisted which do not carry two amino groups are taken as derivatives withat least one additional amino group, and more preferably made from orselected from the following commercially available amino compounds(example of suppliers: Aldrich, ABCR, ACROS, Fluka) which can also beused as comonomers:

-   4-amino-2,3,5,6-tetrafluorobenzoic acid-   4-amino-3,5-diiodobenzoic acid, 3,4-diaminobenzoic acid-   4-amino-3-methylbenzoic acid,-   4-amino-2-chlorobenzoic acid-   4-aminosalicylic acid-   4-aminobenzoic acid-   4-aminophthalic acid-   1-(4-aminophenyl)ethanol-   4-aminobenzyl alcohol-   4-amino-3-methoxybenzoic acid-   4-aminophenyl ethyl carbinol-   4-amino-3-nitrobenzoic acid-   4-amino-3,5-dinitrobenzoic acid-   4-amino-3,5-dichlorobenzoic acid-   4-amino-3-hydroxybenzoic acid-   4-aminobenzyl alcohol hydrochloride-   4-aminobenzoic acid hydrochloride-   pararosaniline base-   4-amino-5-chloro-2-methoxybenzoic acid-   4-(hexafluoro-2-hydroxyisopropyl)aniline-   piperazine-p-amino benzoate-   4-amino-3,5-dibromobenzoic acid-   isonicotinic acid hydrazide p-aminosalicylate salt-   4-amino-3,5-diiodosalicylic acid-   4-amino-2-methoxybenzoic acid-   2-[2-(4-aminophenyl)-2-hydroxy-1-(hydroxymethyl)ethyl]isoindoline-1,3-dione-   4-amino-2-nitrobenzoic acid-   2,4-diaminobenzoic acid-   p-aminobenzoic acid,-   [3, 5-3h]-4-amino-2-methoxybenzoic acid-   L-(+)-threo-2-amino-1-(4-aminophenyl)-1,3-propanediol-   L-(+)-threo-2-(N,N-dimethylamino)-1-(4-aminophenyl)-1,3-propanediol-   ethyl 2-(4-aminophenyl)-3,3,3-trifluoro-2-hydroxypropanoate-   ethyl 2-(4-amino-3-methylphenyl)-3,3,3-trifluoro-2-hydroxypropanoate-   ethyl    2-(4-amino-3-methoxyphenyl)-3,3,3-trifluoro-2-hydroxypropanoate-   3,4-diaminobenzyl alcohol dihydrochloride-   4-aminonaphthalene-1,8-dicarboxylic acid-   4-amino-3-chloro-5-methylbenzoic acid-   4-amino-2,6-dimethylbenzoic acid-   4-amino-3-fluorobenzoic acid-   4-amino-5-bromo-2-methoxybenzenecarboxylic acid-   2,7-diaminofluorene-   4,4′-diaminooctafluorobiphenyl-   3,3′-diaminobenzidine-   3,3′,5,5′-tetramethylbenzidine-   3,3′-dimethoxybenzidine-   o-tolidine-   3,3′-dinitrobenzidine-   2-nitrobenzidine-   3,3′-dihydroxybenzidine-   o-tolidine sulfone-   benzidine,-   3,3′-dichlorobenzidine-   2,2′,5,5′-tetrachlorobenzidine,-   benzidine-3,3′-dicarboxylic acid-   4,4′-diamino-1,1′-binaphthyl-   4,4′-diaminodiphenyl-3,3′-diglycolic acid-   dihydroethidium-   o-dianisidine-   2,2′-dichloro-5,5′-dimethoxybenzidine-   3-methoxybenzidine-   3,3′-dichlorobenzidine (diphenyl-d6),-   2,7-diamino-9-fluorenone-   3,5,3′,5′-tetrabromo-biphenyl-4,4′-diamine-   2,2′-bis(trifluoromethyl)benzidine-   2,2′-dichloro[1,1′-biphenyl]-4,4′-diamine-   3,9-diamino-1,11-dimethyl-5,7-dihydro-dibenzo(a,c)cyclohepten-6-one-   3,3′-bis(trifluoromethyl)benzidine-   dibenzo(1,2)dithiine-3,8-diamine-   3,3′-tolidine-5-sulfonic acid-   3,3′-dichlorobenzidine-d6 tetramethylbenzidine-   3,3′-diaminobenzophenone, 3,3′-diaminodiphenylmethane,-   4,4-bis-(3-amino-4-hydroxyphenyl)-valeric acid-   2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane-   2,2-bis(3-amino-4-methylphenyl)hexafluoropropane tetrabromo    methylenedianiline-   2,7-diamino-9-fluorenone-   2,2-bis(3-aminophenyl)hexafluoropropane-   bis-(3-amino-4-chloro-phenyl)-methanone-   bis-(3-amino-4-dimethylamino-phenyl)-methanone-   3-[3-amino-5-(trifluoromethyl)benzyl]-5-(trifluoromethyl)aniline-   1,5-diaminonaphthalene    or their derivatives, again with the proviso that compounds listed    which do not carry two amino groups are taken as derivatives with at    least one additional amino group.

Preferred examples of additional other diamines (L) are:

ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine,1,5-pentylenediamine, 1,6-hexylenediamine, 1,7-heptylenediamine,1,8-octylenediamine, 1,9-nonylenediamine, 1,10-decylenediamine,1,11-undecylenediamine, 1,12-dodecylenediamine, α,α′-diamino-m-xylene,α,α′-diamino-p-xylene, (5-amino-2,2,4-trimethylcyclopentyl)methylamine,1,2-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane,1,3-bis(methylamino)cyclohexane, 4,9-dioxadodecane-1,12-diamine,3,5-diaminobenzoic acid methyl ester, 3,5-diaminobenzoic acid hexylester, 3,5-diaminobenzoic acid dodecyl ester, 3,5-diaminobenzoic acidisopropyl ester, 4,4′-methylenedianiline, 4,4′-ethylenedianiline,4,4′-diamino-3,3′-dimethyldiphenylmethane,3,3′,5,5′-tetramethylbenzidine, 4,4′-diaminodiphenyl sulfone,4,4′-diaminodiphenyl ether,1,5-diaminonaphthalene,3,3′-dimethyl-4,4′-diaminobiphenyl,3,4′-diaminodiphenyl ether, 3,3′-diaminobenzophenone,4,4′-diaminobenzophenone, 4,4′-diamino-2,2′-dimethylbibenzyl,bis[4-(4-aminophenoxy)phenyl]sulfone, 1,4-bis(4-aminophenoxy)benzene,1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene,2,7-diaminofluorene, 9,9-bis(4-aminophenyl)fluorene,4,4′-methylenebis(2-chloroaniline), 4,4′-bis(4-aminophenoxy)biphenyl,2,2′,5,5′-tetrachloro-4,4′-diaminobiphenyl,2,2′-dichloro-4,4′-diamino-5,5′-dimethoxybiphenyl,3,3′-dimethoxy-4,4′-diaminobiphenyl,4,4′-(1,4-phenyleneisopropylidene)bisaniline,4,4′-(1,3-phenyleneisopropylidene)bisaniline,2,2-bis[4-(4-aminophenoxy)phenyl]propane,2,2-bis[3-(4-aminophenoxy)phenyl]hexafluoropropane,2,2-bis[3-amino-4-methylphenyl]hexafluoropropane,2,2-bis(4-aminophenyl)hexafluoropropane,2,2′-bis[4-(4-amino-2-trifluoromethylphenoxy)phenyl]hexafluoropropane,4,4′-diamino-2,2′-bis(trifluoromethyl)biphenyl, and4,4′-bis[(4-amino-2-trifluoromethyl)phenoxy]-2,3,5,6,2′,3′,5′,6′-octafluorobiphenyl;as well as diamines (L) disclosed in U.S. Pat. No. 6,340,506, WO00/59966 and WO 01/53384, all of which are explicitly incorporatedherein by reference;

The diamine compounds (L) according to the present invention may beprepared using methods that are known to a person skilled in the art.

In addition, preferred diamines (L) are the commercially available oneslisted below:

Polymers

Poly(3,3′,4,4′-benzophenonetetracarboxylicdianhydride-co-4,4′-oxydianiline/1,3-phenylenediamine), amic acidsolutionPoly(3,3′,4,4′-benzophenonetetracarboxylicdianhydride-co-4,4′-oxydianiline/1,3-phenylenediamine), amic acidsolutionPoly(pyromellitic dianhydride-co-4,4′-oxydianiline), amic acid solutionAromatic diamine

-   2,7-diaminofluorene-   1,5-diaminoanthraquinone-   2,6-diaminoanthraquinone-   pararosaniline hydrochloride-   3,6-acridinediamine-   4,4′-diaminooctafluorobiphenyl-   2,2′-dithiodianiline-   3,3′,5,5′-tetramethylbenzidine-   3,3′-diaminodiphenyl sulfone-   4,4′-diamino-2,2′-dimethylbibenzyl-   4,4′-diaminodiphenyl ether-   4,4′-dithiodianiline-   4,4′-diaminodiphenyl sulfone-   4,4′-diaminodiphenylmethane-   4,4′-ethylenedianiline-   3,3′-dimethoxybenzidine-   2,2′-dithiobis(1-naphthylamine)-   3,7-diamino-2-methoxyfluorene-   3,6-diamino-10-methylacridinium chloride-   propidium iodide-   o-dianisidine dihydrochloride-   2,7-diaminofluorene dihydrochloride-   pararosaniline acetate-   3,6-diamino-10-methylacridinium chloride hydrochloride-   proflavine dihydrochloride-   o-tolidine dihydrochloride-   3,3′,5,5′-tetramethylbenzidine dihydrochloride-   3,3′-diaminobenzidine tetrahydrochloride-   4,4′-diaminostilbene dihydrochloride-   4,4′-diaminodiphenylamine sulfate-   proflavine hemisulfate-   2,2′-ethylenedianiline diphosphate-   1,5-diamino-4,8-dihydroxyanthraquinone-   o-tolidine-   3,3′-diaminobenzophenone-   3,3′-diaminodiphenylmethane-   3,4′-diaminodiphenylmethane-   2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane-   4,4′-diamino-1,1′-dianthramide-   3,3′-dinitrobenzidine-   4,4′-diamino-5,5′-dimethyl-2,2′-biphenyldisulfonic acid-   4,4′-diaminostilbene-2,2′-disulfonic acid-   3-amino-4-hydroxyphenyl sulfone-   4,4-bis-(3-amino-4-hydroxyphenyl)-valeric acid-   2,2′-diamino-4,4′-difluorobibenzyl-   2-amino-4-chlorophenyl disulfide-   3,3′-(decamethylenedioxy)dianiline-   3,3′-(pentamethylenedioxy)dianiline-   4-(p-aminoanilino)-3-sulfoaniline-   4-[3-(4-aminophenoxy)propoxy]aniline-   2-nitrobenzidine-   benzidine-3-sulfonic acid-   4,4′-diaminodiphenyl sulfide-   4,4′-diaminobenzanilide-   n,n′-bis(3-aminophenylsulfonyl)ethylenediamine-   2,2′-biphenyldiamine-   3,4′-diaminodiphenyl ether-   proflavine hemisulphate-   phenosafranin-   4,4′-diaminobenzophenone-   2,2-bis(4-aminophenyl)hexafluoropropane-   2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane-   2,2-bis(3-amino-4-methylphenyl)hexafluoropropane-   3,3′-dihydroxybenzidine-   3,3′-diamino-4,4′-dihydroxybiphenyl-   4,4′-bis(4-aminophenoxy)biphenyl-   2,2-bis[4-(4-aminophenoxy)phenyl]propane-   1,4-bis(4-aminophenoxy)benzene-   1,3-bis(4-aminophenoxy)benzene-   bis[4-(4-aminophenoxy)phenyl]sulfone-   9,9-bis(4-aminophenyl)fluorene-   o-tolidine sulfone-   benzidine-   3,3′-dichlorobenzidine dihydrochloride-   benzidine dihydrochloride-   3,6-thioxanthenediamine-10,10-dioxide-   4,4′-diamino-2,2′-biphenyldisulfonic acid-   4,4′-azodianiline-   2,5-bis-(4-aminophenyl)-(1,3,4)oxadiazole-   3,3′-dimethylnaphthidine-   benzidine sulfate-   1,3-bis(3-aminophenoxy)benzene-   3,3′-dichlorobenzidine-   2,2′,5,5′-tetrachlorobenzidine-   4,4′-diamino-1,1′-binaphthyl-   diamine bordeaux-   benzoflavin-   chrysaniline-   2,2′-thiobis(5-aminobenzenesulfonic acid)-   4,4′-methylene-bis(2-chloroaniline)-   tetrabromo methylenedianiline-   4,4′-diamino-3,3′-dinitrodiphenyl ether-   benzidine pyrophosphate-   3,6-diaminothioxanthene-10-dioxide, dihcl-   4,4″-diamino-p-terphenyl-   1,8-diamino-4,5-dihydroxyanthraquinone-   bis(p-aminophenoxy)dimethylsilane-   bis[4-(3-aminophenoxy)phenyl]sulfone-   4,4′-methylenedi-2,6-xylidine-   2-aminobenzaldehyde-ethylene-diimine-   3-methylbenzidine dihydrochloride-   3,3′-diethylbenzidine dihydrochloride-   3,6-diaminoacridine hydrochloride-   4,4′-diamino-5,5′-dimethyl-2,2′-biphenyl disulfonic acid disodium    salt-   4,4′-methylenebis(3-chloro-2,6-diethylaniline)-   4,4′-methylene-bis-(2,6-diethylaniline)-   4,4′-methylenebis-(2,6-diisopropylaniline)-   toluoylenediamine-   3,8-diamino-6-phenylphenanthridine-   thionin perchlorate-   dihydroethidium-   thionin-   4,4-diamino benzene sulfonyl anilide-   o-dianisidine hcl-   2,2′-dichloro-5,5′-dimethoxybenzidine-   3-methoxybenzidine-   2,2′-(hexamethylenedioxy)dianiline-   2,2′-(pentamethylenedioxy)dianiline-   2,2′-(ethylenedioxy)dianiline-   4-[4-(4-aminophenoxy)butoxy]aniline-   2,2′-diamino-4′-methoxy-4-methylbenzanilide-   5,5′-dimethyl-2,2′-dinitrobenzidine-   n,n′-bis(2-aminophenyl)-1,3-propanediamine-   3,4′-diaminochalcone-   2,3′,4,5′,6-pentaphenyl-3,4′-biphenyldiamine-   2-([1-(4-(1-[(2-aminophenyl)thio]-2-nitroethyl)phenyl)-2-nitroethyl]thio)an    ilin-   2-((2-[(2-aminophenyl)thio]ethyl)thio)aniline-   2-((4-[(2-aminophenyl)thio]but-2-enyl)thio)aniline-   4,4′-diamino-3,3′-dimethyldiphenyl methane-   2,2′-diamino-bibenzyl-   trimethylene bis(4-aminobenzoate)-   fluoresceinamine-   benzidines mixture-   3-nitro-4,4′-methylenedianiline-   4,4-diamino-2,2′-dichlorodiphenyl disulfide-   1,6-diaminopyrene-   1,8-diaminopyrene-   3,6-diaminocarbazole-   4,4′(5′)-diamino-[2,4]-dibenzo-18-crown-6,dihydrochloride-   4,4′-diaminostilbene-2,2′-disulfonic acid, disodium salt-   (r)-(+)-2,2′-diamino-1,1′-binaphthyl-   proflavine hemisulfate dihydrate-   3,6-diaminoacridine hemisulfate hemihydrate-   dimidium bromide monohydrate-   o-tolidine dihydrochloride hydrate-   3,3′,5,5′-tetramethylbenzidine dihydrochloride hydrate-   3,3′-diaminobenzidine tetrahydrochloride dihydrate-   3,6-[bis(4-amino-3-(sodiumsulphonato)phenylamino)]-2,5-dichloro    4-benzoquinone-   2,2′-dimethylbenzidine hydrochloride-   2,2′-(phenylmethylenebis)bis(4-methylaniline)-   3,4′-diaminobiphenyl-   2,7-diamino-9-fluorenone-   n,n′-bis(2-aminophenyl)oxamide-   2-[2-(2-aminophenyl)diaz-1-enyl]aniline-   3,5,3′,5′-tetrabromo-biphenyl-4,4′-diamine-   n,n′-bis(4-aminophenyl)-1,3-bis(aminomethyl)benzene dihydrochloride-   4′,4″(5″)-diaminodibenzo-15-crown-5-   2,2′-bis(trifluoromethyl)benzidine-   bis(4-amino-2,3-dichlorophenyl)methane-   alpha,alpha′-bis(4-aminophenyl)-1,4-diisopropylbenzene-   2,2-bis(3-aminophenyl)hexafluoropropane-   3,10-diamino-6,13-dichlorobenzo[5,6][1,4]oxazino[2,3-b]phenoxazine-4,11-dis    ulfo-   n1-(2-amino-4-methylphenyl)-2-aminobenzamide-   n1-(2-amino-4-chlorophenyl)-2-aminobenzamide-   2,2′-dichloro[1,1′-biphenyl]-4,4′-diamine-   4,4′(5′)-diaminodibenzo-15-crown-5 dihydrochloride-   rcl s19, 413-1-   bis-(4-amino-3-nitro-phenyl)-methanone-   bis-(3-amino-4-chloro-phenyl)-methanone-   bis-(3-amino-4-dimethylamino-phenyl)-methanone-   n,n′-bis-(4-amino-2-chloro-phenyl)-isophthalamide-   n,n′-bis-(4-amino-2-chloro-phenyl)-terephthalamide-   3,9-diamino-1,11-dimethyl-5,7-dihydro-dibenzo(a,c)cyclohepten-6-one-   2-aminobenzaldehyde n-[(z)-(2-aminophenyl)methylidene]hydrazone-   3,3′-bis(trifluoromethyl)benzidine-   dicarboxidine 2 hcl-   4,4′-(1,3-phenylenediisopropylidene)bisaniline-   1,4-phenylenebis[[4-(4-aminophenoxy)phenyl]methanone]-   2-((5-[(2-aminophenyl)thio]-3,4-dinitro-2-thienyl)thio)aniline-   n′1-(2-aminobenzoyl)-2-aminobenzene-1-carbohydrazide-   2-[4-(5-amino-1h-benzimidazol-2-yl)phenyl]-1h-benzimidazol-5-amine-   4-[4-(4-aminophenoxy)-2,3,5,6-tetrafluorophenoxy]aniline-   3,3′-dinitro-4,4′-diaminodiphenyl sulfone-   3,3′,4,4′-tetraaminodiphenylsulfone-   4-[1-(4-aminophenyl)-1-methylethyl]aniline-   3,3-diamino diphenyl urea-   bis(4-aminophenyl)acetylene-   dibenzo(1,2)dithiine-3,8-diamine-   ethidium homodimer-2-   4,4′-bis-(2-aminobenzenesulfonyl)bis-phenolester-   neopentyl glycol bis(4-aminophenyl)ether-   2,2′-oxydianiline-   4,4′-diaminodiphenylamine-2,2-disulphonic acid-   4,4-diamino diphenyl urea-   3,3′-tolidine-5-sulfonic acid-   n1-(3-[(2-aminobenzoyl)amino]propyl)-2-aminobenzamide-   2-((6-[(2-aminophenyl)sulfanyl]-5-nitro-2-pyridyl)sulfanyl)aniline-   2-((6-amino-1,3-benzothiazol-2-yl)dithio)-1,3-benzothiazol-6-ylamine-   tetramethylbenzidine-   2-([6-[(2-aminophenyl)sulfanyl]-3,5-di(trifluoromethyl)-2-pyridyl]sulfanyl)anil-   3,6-diaminothioxanthene-10-dioxide dihydrochloride-   m-tolidine dihydrochloride hydrate-   2-amino-n-[2-amino-4-(trifluoromethyl)phenyl]-5-methylbenzamide-   2-([2-[(2-aminophenyl)thio]-6-nitro-4-(trifluoromethyl)phenyl]thio)aniline-   2-[(3-([(2-aminophenyl)thio]methyl)-2,4,6-trimethylbenzyl)thio]aniline-   3-[3-amino-5-(trifluoromethyl)benzyl]-5-(trifluoromethyl)aniline-   2-((5-[(2-aminophenyl)thio]-4-chloro-2-nitrophenyl)thio)aniline-   4-(1-(4-aminophenyl)-2-[4-(dimethylamino)phenyl]vinyl)aniline-   1,5-bis(4-aminophenoxy)pentane-   2,3′-dichlorobenzidine dihydrochloride-   3,3′-diamono-4,4′-dichlorodiphenyl sulfone-   3-(bis-(4-amino-phenyl)-methyl)-2,3-dihydro-isoindol-1-one-   4,4-diamino diphenyl-2-sulphonic acid-   4,4′-diamino-diphenylene-cycylohexane-   4,5′-diamino-(1,1′)bianthracenyl-9,10,9′,10′-tetraone

Alicyclic Diamines

-   4,4′-methylenebis(cyclohexylamine)-   4,4′-methylenebis(2-methylcyclohexylamine)

Aliphatic Diamines

-   1,8-diamino-p-menthane-   4,4′-methylenebis(cyclohexylamine)-   d-cystine-   l-cystine dimethyl ester dihydrochloride-   neamine-   bis(2-aminopropyl)amine-   (h-cys-beta-na)2 2 hcl-   l-cystine dibenzyl ester ditosylate-   1,4-diaminocyclohexane-   (h-cys-pna)2-   dl-2-aminopropionic anhydride-   l-cystine(di-b-naphthylamide)hydrochloride-   l-cystine-bis-p-nitroanilide dihydrobromide-   l-cystine diethyl ester dihydrochloride-   trans-1,4-cyclohexanediamine-   4,4′-methylenebis(2-methylcyclohexylamine)-   l-leucinethiol, oxidized dihydrochloride-   1,3-diaminoadamantane dihydrochloride-   l-leucinethiol disulfide 2 hcl-   l-cystine disodium salt, monohydrate-   l-homocystine methylester hydrochloride-   1,3-adamantanediamine-   tetracyclo[8.2.1.1(8,11).0(2,7)]tetradeca-2,4,6-triene-10,11-diamine-   tricyclo[3.3.1.0(3,7)]nonane-3,7-diamine

From the class of commercially available diamines (L) preferred are thebelow listed ones:

Alicyclic Diamines

-   4,4′-methylenebis(cyclohexylamine)-   4,4′-methylenebis(2-methylcyclohexylamine)

Aliphatic Diamines

-   4,4′-methylenebis(cyclohexylamine)-   1,4-diaminocyclohexane-   trans-1,4-cyclohexanediamine-   4,4′-methylenebis(2-methylcyclohexylamine)-   1,3-adamantanediamine

Aromatic Diamines

-   2,7-diaminofluorene-   2,6-diaminoanthraquinone-   4,4′-diaminooctafluorobiphenyl-   4,4′-diaminodiphenyl ether-   4,4′-dithiodianiline-   4,4′-diaminodiphenylmethane-   4,4′-ethylenedianiline-   3,3′-dimethoxybenzidine-   o-tolidine-   3,3′-diaminobenzophenone-   3,3′-diaminodiphenylmethane-   3,4′-diaminodiphenylmethane-   2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane-   4-[3-(4-aminophenoxy)propoxy]aniline-   4,4′-diaminodiphenyl sulfide-   4,4′-diaminobenzophenone-   2,2-bis(4-aminophenyl)hexafluoropropane-   4,4′-bis(4-aminophenoxy)biphenyl-   2,2-bis[4-(4-aminophenoxy)phenyl]propane-   1,4-bis(4-aminophenoxy)benzene-   1,3-bis(4-aminophenoxy)benzene-   bis[4-(4-aminophenoxy)phenyl]sulfone-   9,9-bis(4-aminophenyl)fluorene-   benzidine-   4,4′-azodianiline-   1,3-bis(3-aminophenoxy)benzene-   4,4′-diamino-1,1′-binaphthyl-   4,4″-diamino-p-terphenyl-   bis(p-aminophenoxy)dimethylsilane-   4-[4-(4-aminophenoxy)butoxy]aniline-   3,4′-diaminochalcone-   trimethylene bis(4-aminobenzoate)-   3,4′-diaminobiphenyl-   2,7-diamino-9-fluorenone-   4′,4″(5″)-diaminodibenzo-15-crown-5-   2,2′-bis(trifluoromethyl)benzidine-   alpha,alpha′-bis(4-aminophenyl)-1,4-diisopropylbenzene-   3,3′-bis(trifluoromethyl)benzidine-   4,4′-(1,3-phenylenediisopropylidene)bisaniline-   1,4-phenylenebis[[4-(4-aminophenoxy)phenyl]methanone]-   4-[4-(4-aminophenoxy)-2,3,5,6-tetrafluorophenoxy]aniline-   4-[1-(4-aminophenyl)-1-methylethyl]aniline-   neopentyl glycol bis(4-aminophenyl)ether-   4,4-diamino diphenyl ur-   1,5-bis(4-aminophenoxy)pentane

From the class of commercially available diamines (L) more preferred arethe below listed ones:

Aromatic Diamines

-   2,7-diaminofluorene-   4,4′-diaminooctafluorobiphenyl-   4,4′-diaminodiphenyl ether-   4,4′-diaminodiphenylmethane-   4,4′-ethylenedianiline-   3,3′-diaminobenzophenone-   4-[3-(4-aminophenoxy)propoxy]aniline-   4,4′-diaminodiphenyl sulfide-   4,4′-diaminobenzophenone-   2,2-bis(4-aminophenyl)hexafluoropropane-   4,4′-bis(4-aminophenoxy)biphenyl-   2,2-bis[4-(4-aminophenoxy)phenyl]propane-   1,4-bis(4-aminophenoxy)benzene-   1,3-bis(4-aminophenoxy)benzene-   9,9-bis(4-aminophenyl)fluorene-   benzidine-   bis(p-aminophenoxy)dimethylsilane-   4-[4-(4-aminophenoxy)butoxy]aniline-   3,4′-diaminochalcone-   trimethylene bis(4-aminobenzoate)-   3,4′-diaminobiphenyl-   2,7-diamino-9-fluorenone-   4′,4″(5″)-diaminodibenzo-15-crown-5-   4-[4-(4-aminophenoxy)-2,3,5,6-tetrafluorophenoxy]aniline-   4-[1-(4-aminophenyl)-1-methylethyl]aniline-   1,5-bis(4-aminophenoxy)pentane

Aliphatic Diamines

-   4,4′-methylenebis(cyclohexylamine)-   1,4-diaminocyclohexane

Alicyclic Diamines

-   4,4′-methylenebis(cyclohexylamine)

A further embodiment of the present invention is a compositioncomprising at least one diamine (I) and optionally at least one furtherdiamine, which is different from (I) or/and an additive.

Preferably, the further diamine is of formula (L).

Additives such as silane-containing compounds and epoxy-containingcrosslinking agents may be added.

Suitable silane-containing additives are described in Plast. Eng. 36(1996), (Polyimides, fundamentals and applications), Marcel Dekker, Inc.

Suitable epoxy-containing cross-linking additives include4,4′-methylene-bis-(N,N-diglycidylaniline), trimethylolpropanetriglycidyl ether, benzene-1,2,4,5-tetracarboxylic acid1,2,4,5-N,N′-diglycidyldiimide, polyethylene glycol diglycidyl ether,N,N-diglycidylcyclohexylamine and the like.

Additional additives are photo-sensitizers, photo-radical generators,cationic photo-initiators.

Suitable photo-active additives include 2,2-dimethoxyphenylethanone, amixture of diphenylmethanone and N,N-dimethylbenzenamine or ethyl4-(dimethylamino)-benzoate, xanthone, thioxanthone, Irgacure® 184, 369,500, 651 and 907 (Ciba), Michler's ketone, triaryl sulfonium salt andthe like.

Further the present invention relates to a process for the preparationof a diamine compound (XII) as defined above comprising contacting acompound of formula (XIV)

with a dinitro compound of formula (XVI)

and then converting the obtained dinitro compound of formula (XVIa)

in the corresponding diamino compound of formula (XII)

wherein F, x₁, n₁, n, B, D, X, Y, Z¹, L, u₁, u₂ and S¹ have the samemeanings and preferences as given above, and wherein D1 has the samemeaning and preferences as D as given above, with the proviso that thetwo amino groups of D are replaced by two nitro groups.

The reaction between compounds (XIV) and (XVI) can be conducted in manyknown ways (see J. March, Advanced Organic Chemistry, second edition,pages 363 and 365).

Usually, compounds (XIV) and (XVI) are contacted with a dehydratingagent.

Commonly known dehydrating agents can be used. Preferred are EDC,1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride or DCC,dicyclohexylcarbodiimide, trifluoroacetic anhydride, H₃BO₃—H₂SO₄,polymer-protected AlCl₃, pyridinium salts-Bu₃N orN,N-carbonyldiimidazole.

In general, the reaction of compounds (XIV) and (XVI) is conducted in asolvent.

Usually organic solvents, such as for example toluene, xylene, pyridine,halogenalkane, such as dichlormethan, trichlorethan, acetone ordimethylformamide are used.

The conversion of nitro compounds to amino compounds is commonly knownand for example described J. March, Advanced Organic Chemistry, 1977,pages 1125 and 1126). Further, the conversion can be conducted inanalogy to the process described in WO 98/13331 and WO 96/36597.

Further, the present invention relates to compounds of formulae (XIV)and (XVI), and (XVIa) as given above.

In addition, the present invention relates to polymer, copolymer andoligomer comprising diamine (I) as one of the basic building blocks.

Preferred polymer, copolymer and oligomer comprise diamine (I) and atetracarboxylic acid anhydride as basic building blocks.

Preferably, the polymer, copolymer or oligomer is comprising diamine (I)as one basic building block are in the context of the invention apolyamic acid, polyamic ester, polyimide or a mixture thereof,preferably a mixture of polyamic acid and polyamic ester and/orpolyimide. More preferred is a mixture of polyamic acid and polyimide.

In the context of the present invention the term “polyimide” has themeaning of partially or complete imidisated polyamic acid or polyamicester. In analogy, the term “imidisation” has in the context of thepresent invention the meaning of partially or complete imidisation.

Preferably, the tetracarboxylic acid anhydride is of formula (V)

wherein:T represents a tetravalent organic radical.

The tetravalent organic radical T is preferably derived from analiphatic, alicyclic or aromatic tetracarboxylic acid dianhydride.

Preferred examples of aliphatic or alicyclic tetracarboxylic aciddianhydrides are:

-   1,1,4,4-butanetetracarboxylic acid dianhydride,-   ethylenemaleic acid dianhydride,-   1,2,3,4-cyclobutanetetracarboxylic acid dianhydride,-   1,2,3,4-cyclopentanetetracarboxylic acid dianhydride,-   2,3,5-tricarboxycyclopentylacetic acid dianhydride,-   3,5,6-tricarboxynorbornylacetic acid dianhydride,-   2,3,4,5-tetrahydrofurantetracarboxylic acid dianhydride,-   rel-[1S,5R,6R]-3-oxabicyclo[3.2.1]octane-2,4-dione-6-spiro-3′-(tetrahydrofuran2′,5′-dione),-   4-(2,5-dioxotetrahydrofuran-3-yl)tetrahydronaphthalene-1,2-dicarboxylicacid    dianhydride,-   5-(2,5-dioxotetrahydrofuran-3-yl)-3-methyl-3-cyclohexene-1,2-dicarboxylicacid    dianhydride,-   bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride,-   bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic acid dianhydride,-   1,8-dimethylbicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid    dianhydride, pyromellitic acid dianhydride,-   3,3′,4,4′-benzophenonetetracarboxylic acid dianhydride,-   4,4′-oxydiphthalic acid dianhydride,-   3,3′,4,4′-diphenylsulfonetetracarboxylic acid dianhydride,-   1,4,5,8-naphthalenetetracarboxylic acid dianhydride,-   2,3,6,7-naphthalenetetracarboxylic acid dianhydride,-   3,3′,4,4′-dimethyldiphenylsilanetetracarboxylic acid dianhydride,-   3,3′,4,4′-tetraphenylsilanetetracarboxylic acid dianhydride,-   1,2,3,4-furantetracarboxylic acid dianhydride,-   4,4′-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride,-   4,4′-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride,-   4,4′-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride,-   3,3′,4,4′-biphenyltetracarboxylic acid dianhydride,-   ethylene glycol bis(trimellitic acid) dianhydride,-   4,4′-(1,4-phenylene)bis(phthalic acid) dianhydride,-   4,4′-(1,3-phenylene)bis(phthalic acid) dianhydride,-   4,4′-(hexafluoroisopropylidene)diphthalic acid dianhydride,-   4,4′-oxydi(1,4-phenylene)bis(phthalic acid) dianhydride, and-   4,4′-methylenedi(1,4-phenylene)bis(phthalic acid) dianhydride.

Preferred examples of aromatic tetracarboxylic acid dianhydrides are:

-   pyromellitic acid dianhydride,-   3,3′,4,4′-benzophenonetetracarboxylic acid dianhydride,-   4,4′-oxydiphthalic acid dianhydride,-   3,3′,4,4′-diphenylsulfonetetracarboxylic acid dianhydride,-   1,4,5,8-naphthalenetetracarboxylic acid dianhydride,-   2,3,6,7-naphthalenetetracarboxylic acid dianhydride,-   3,3′,4,4′-dimethyldiphenylsilanetetracarboxylic acid dianhydride,-   3,3′,4,4′-tetraphenylsilanetetracarboxylic acid dianhydride,-   1,2,3,4-furantetracarboxylic acid dianhydride,-   4,4′-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride,-   4,4′-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride,-   4,4′-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride,-   3,3′,4,4′-biphenyltetracarboxylic acid dianhydride,-   ethylene glycol bis(trimellitic acid) dianhydride,-   4,4′-(1,4-phenylene)bis(phthalic acid) dianhydride,-   4,4′-(1,3-phenylene)bis(phthalic acid) dianhydride,-   4,4′-(hexafluoroisopropylidene)diphthalic acid dianhydride,-   4,4′-oxydi(1,4-phenylene)bis(phthalic acid) dianhydride,-   4,4′-methylenedi(1,4-phenylene)bis(phthalic acid) dianhydride,-   and the like.

More preferably the tetracarboxylic acid dianhydrides used to form thetetravalent organic radical T are selected from:

-   1,2,3,4-cyclobutanetetracarboxylic acid dianhydride,-   1,2,3,4-cyclopentanetetracarboxylic acid dianhydride,-   2,3,5-tricarboxycyclopentylacetic acid dianhydride,-   5-(2,5-dioxotetrahydrofuran-3-yl)-3-methyl-3-cyclohexene-1,2-dicarboxylic    acid dianhydride,-   4-(2,5-dioxotetrahydrofuran-3-yl)tetrahydronaphthalene-1,2-dicarboxylic    acid dianhydride,-   4,4′-(hexafluoroisopropylidene)diphthalic acid dianhydride and    bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride.

The polymer, copolymer or oligomer, especially the polyamic acid,polyamic acid ester and polyimide and mixtures thereof may be preparedin line with known methods, such as those described in Plast. Eng. 36(1996), (Polyimides, fundamentals and applications), Marcel Dekker, Inc.

For example, the amidisation, poly-condensation reaction for thepreparation of the polyamic acids is carried out in solution in a polaraprotic organic solvent, such as γ-butyrolactone, N,N-dimethylacetamide,N-methylpyrrolidone or N,N-dimethyl-formamide. In most cases equimolaramounts of the anhydride and the diamine are used, i.e. one amino groupper anhydride group. If it is desired to stabilize the molecular weightof the polymer, copolymer or oligomer, it is possible for that purposeto either add an excess or a less-than-stoichiometric amount of one ofthe two components or to add a mono-functional compound in the form of adicarboxylic acid monoanhydride or in the form of a monoamine. Examplesof such mono-functional compounds are maleic acid anhydride, phthalicacid anhydride, aniline and the like. Preferably the reaction is carriedout at temperatures of less than 100° C.

The imidisation, cyclisation of the polyamic acids to form thepolyimides can be carried out by heating, i.e. by condensation withremoval of water or by other imidisation reactions using appropriatereagents.

Partially imidisation is achieved for example, if the imidisation iscarried out purely thermally, the imidisation of the polyamic acids maynot always be complete, i.e. the resulting polyimides may still containproportions of polyamic acid.

Complete imidisation reactions are carried out at temperatures between60 and 250° C., preferably at temperatures of less than 200° C.

In order to achieve imidisation at lower temperatures additionalreagents that facilitate the removal of water are added to the reactionmixture. Such reagents are, for example, mixtures consisting of acidanhydrides, such as acetic acid anhydride, propionic acid anhydride,phthalic acid anhydride, trifluoroacetic acid anhydride or tertiaryamines, such as triethylamine, trimethylamine, tributylamine, pyridine,N,N-dimethylaniline, lutidine, collidine etc. The amount ofaforementioned additional reagents that facilitate the removal of wateris preferably at least four equivalents of acid anhydride and twoequivalents of amine per equivalent of polyamic acid to be condensed.

The imidization degree of each polymer used in the liquid crystalalignment agent of the invention can be arbitrarily adjusted bycontrolling the catalyst amount, reaction time and reaction temperatureemployed in production of the polymer. In the present description,“imidization degree” of polymer refers to a proportion (expressed in %)of the number of recurring units of polymer forming an imide ring or anisoimide ring to the number of total recurring units of polymer. In thepresent description, the imidization degree of a polyamic acid notsubjected to dehydration and ring closure is 0%. The imidization degreeof each polymer is determined by dissolving the polymer in deuterateddimethyl sulfoxide, subjecting the resulting solution to ¹H-NMRmeasurement at a room temperature using tetramethylsilane as a standardsubstance, and calculating from the following formula.

Imidization degree(%)=1−(A ¹ /A2×B)×100

A¹: Peak area based on protons of NH groups (in the vicinity of 10 ppm)A²: Peak area based of one proton of acrylate double bond (in thevicinity of 6.5 ppm).B: Proportion of the number of acrylate protons to one proton of NHgroup in the polymer precursor

The imidization degree is usually in the range of 1 to 99%, preferably 5to 50%, more preferably 10 to 40%.

The present invention concerns a process for the preparation of apolymer, copolymer or oligomer comprising polymerisation of a diamine(I).

Preferably the polymerisation of a diamine (I) comprises

-   -   a) amidisation of at least one diamine (I) to polyamic acid or a        polyamic ester, and    -   b) imidisation of the obtained polyamic acid or ester, to a        polyimide, or    -   c) imidisation of the diamine (I) to polyimide.

In a more preferred embodiment of the invention, the polymersiation ofthe diamine comprises the amidsation of at least one diamine (I) withtetracarboxylic acid anhydride, preferably tetracarboxylic acidanhydride (V), and/or the imidisation, preferably by elevatedtemperature.

In a further more preferred embodiment of the invention, thepolymersiation of the diamine comprises the amidsation of a diamine (I)with tetracarboxylic acid anhydride, preferably tetracarboxylic acidanhydride (V), and/or the imidisation, preferably by elevatedtemperature, and wherein the amidisation and/or imidisation isoptionally conducted

-   -   in the presence of additives as given above, and/or    -   in the presence of a further diamine, which is different from        that of formula (I), preferably in the presence of at least one        diamine (L) and/or    -   in the presence of a further polymer, copolymer or oligomer        comprising as one basic building block a diamine (L), or a        further polymer, copolymer or oligomer, which is different from        a polyamic acid, polyamic ester or a polyimide, more preferably        a further polymer, copolymer or oligomer, which is selected from        the group of which is selected from the group of polymers        include polyacrylates, polymethacrylates, polyacrylamides,        polymethacrylamides, polyvinylether and polyvinylester,        polyallylether and ester, polystyrenes, polysiloxanes,        polyimides, polyamic acids and their esters, polyamidimides,        polymaleic acids, polyfumaric acids polyurethanes and        derivatives thereof.

Preferably, the further polymer, copolymer or oligomer comprises asbasic building block a diamine (L) and a tetracarboxylic acid anhydride,preferably a tetracarboxylic acid anhydride of formula (V).

This polymer, copolymer or oligomer is prepared in analogy to thepolymer, copolymer or oligomer of the invention comprising diamine (I).

The imididation is conducted after or during amidisation. In general,the imidisation is conducted after amidisation.

Preferred is the partially imidisation of polyamic acid or polyamicester.

If the polymer is prepared only by imidisation, diamine (I) will becontacted with an imidisation compound, with at least two polymerisablefunctional groups, such as for example, carbonyl groups or halogengroups.

More preferably, the present invention concerns a process for thepreparation of a polymer, copolymer or oligomer comprisingpolymerisation of a diamine (I) and tetracarboxylic acid anhydride,preferably tetracarboxylic acid anhydride (V).

Another embodiment of the present invention relates to a copolymercomprising diamine (I). Preferred is a copolymer, comprising at leasttwo diamines (I).

A further embodiment of the present invention relates to a polymer,copolymer or oligomer, or to blends obtainable according to theprocesses and preferred processes of the invention.

Preferably, blends are obtainable by reaction of at least two differentdiamine (I), or by reaction of at least one diamine (I) with a polymer,copolymer or oligomer comprising as basic building block at least onediamine (L).

Preferably, the present invention concerns polymer, copolymer oroligomer, comprising in their polymer-, copolymer- oroligomer-side-chains at least one photo-reactive group. Preferably, thephoto-reactive group of the side chains are photo-isomerized and/orcrosslinked, more preferably photo-dimerized, by exposure to aligninglight.

The term photoreactive groups has the meaning of groups, which are ableto react by interaction with light.

The treatment with aligning light may be conducted in a single step orin several separate steps. In a preferred embodiment of the inventionthe treatment with aligning light is conducted in a single step.

In the context of the present invention photo-reactive group haspreferably the meaning of a dimerizable, isomerizable, polymerizableand/or cross-linkable group.

In the context of the present invention, aligning light is light ofwavelengths, which can initiate photoalignment. Preferably, thewavelengths are in the UV-A, UVB and/or UV/C-range, or in the visiblerange. It depends on the photoalignment compound, which wavelengths areappropriate. Preferably, the photo-reactive groups are sensitive tovisible and/or UV light. A further embodiment of the invention concernsthe generating of aligning light by laser light.

The instant direction of the aligning light may be normal to thesubstrate or at any oblique angle.

For generating tilt angles, preferably the aligning light is exposedfrom oblique angles.

More preferably, aligning light is at least partially linearlypolarized, elliptically polarized, such as for example circularypolarized, or non-polarized; most preferably at least circulary orpartially linearly polarized light, or non-polarized light exposedobliquely. Especially, most preferred aligning light denotessubstantially polarised light, especially linearly polarised light; oraligning light denotes non-polarised light, which is applied by anoblique irradiation.

In a more preferred embodiment of the invention the polymer, copolymeror oligomer is treated with polarised light, especially linearlypolarised light, or by oblique radiation with non-polarised light.

Further preferred are polymers, copolymers or oligomers of the presentinvention,

-   -   wherein at least 30%, preferably at least 75% of the repeating        units include a side chain with a photo-reactive group; and/or    -   wherein, the photo-reactive groups are able to undergo        photo-dimerisation, preferably photo-cyclisation, in particular        [2+2]-photo-cyclisation; and/or    -   wherein the polymer or oligomer is a polymer gel or a polymer        network, or an oligomer gel or an oligomer network,        respectively; and/or    -   wherein the polymer, copolymer or oligomer has an intrinsic        viscosity in the range of 0.05 to 10 dL/g, preferably in the        range of 0.05 to 5 dL/g; and/or    -   wherein the polymer, copolymer or oligomer contains from 2 to        2000 repeating units, especially from 3 to 200 repeating units;        and/or    -   wherein the polymer, copolymer or oligomer is in the form of a        homopolymer or of a copolymer, preferably of a statistical        copolymer; and/or    -   wherein the polymer, copolymer or oligomer is cross-linkable or        cross-linked;

A further preferred embodiment of the present invention concernspolymers, copolymers or oligomers, having an intrinsic viscositypreferably in the range of 0.05 to 10 dL/g, more preferably in the rangeof 0.05 to 5 dL/g. Herein, the intrinsic viscosity (η_(inh)=Inη_(rel)/C) is determined by measuring a solution containing a polymer oran oligomer in a concentration of 0.5 g/100 ml solution for theevaluation of its viscosity at 30° C. using N-methyl-2-pyrrolidone assolvent.

In addition, a preferred embodiment of the present invention concernspolymers, copolymers or oligomers, containing from 2 to 2000 repeatingunits, especially from 3 to 200 repeating units.

The side-chain polymers or oligomers according the invention can bepresent in the form of homopolymers as well as in the form ofcopolymers. The term “copolymers” is to be understood as meaningespecially statistical copolymers.

Further, the present invention concerns a composition, especially ablend, comprising

-   -   a polymer, copolymer or oligomer according to definition and        preferences of the invention, comprising at least a diamine (I)        as basic building block, or    -   a polymer, copolymer or oligomer according to definition and        preferences of the invention, obtainable by the processes of the        invention, and    -   preferably in addition comprising and a further diamine, which        is different from diamine (I), preferably a diamine (L).

The further polymer, copolymer or oligomer comprising as one basicbuilding block a diamine (L) has the same preferences as given above.

Preferably, the present invention concerns a composition, especially ablend, comprising

-   -   a polymer, copolymer or oligomer according to definition and        preferences of the invention, comprising at least a diamine (I)        as basic building block, or    -   a polymer, copolymer or oligomer according to definition and        preferences of the invention, obtainable by the processes of the        invention,    -   and/or a further polymer, copolymer or oligomer comprising as        one basic building block a further diamine, which is different        from diamine (I), preferably a diamine (L), or a further        polymer, copolymer or oligomer, which is different from a        polyamic acid, polyamic ester or a polyimide, more preferably a        further polymer, copolymer or oligomer, which is selected from        the group of polyacrylate, polystyrol, polyester, polyurethane,        polyethylene, poylpopylen, polyvinylchloride,        polytetrafluoroethylen, polycabonate, polyterephthalate and        dendrimere.

Further preferably, the present invention concerns a composition,especially a blend, comprising

-   -   a polymer, copolymer or oligomer according to definition and        preferences of the invention, comprising at least a diamine (I)        as basic building block, or    -   a polymer, copolymer or oligomer according to definition and        preferences of the invention, obtainable by the processes of the        invention,    -   and optionally a further diamine, which is different from        diamine (I), preferably a diamine (L),    -   and an additive, preferably silane-containing compounds,    -   and/or a further polymer, copolymer or oligomer comprising as        one basic building block a further diamine, which is different        from diamine (I), preferably at least one diamine (L),    -   and/or a further polymer, copolymer or oligomer, which is        different from a polyamic acid, polyamic ester or a polyimide,        more preferably a further polymer, copolymer or oligomer, which        is selected from the group of polymers include polyacrylates,        polymethacrylates, polyacrylamides, polymethacrylamides,        polyvinylether and polyvinylester, polyallylether and ester,        polystyrenes, polysiloxanes, polyimides, polyamic acids and        their esters, polyamidimides, polymaleic acids, polyfumaric        acids polyurethanes and derivatives thereof,    -   and/or photo-active polymers, photo-active oligomers and/or        photo-active monomers,    -   and/or cross-linking agents, preferably epoxy-containing        cross-linking agents, most preferably selected from the group:    -   4,4′-methylene-bis-(N,N-diglycidylaniline), trimethylolpropane        triglycidyl ether, benzene-1,2,4,5-tetracarboxylic acid        1,2,4,5-N,N′-diglycidyldiimide, polyethylene glycol diglycidyl        ether, N,N-diglycidylcyclohexylamine.

The polymers or oligomers according to the invention may be used in formof polymer layers or oligomer layers alone or in combination with otherpolymers, oligomers, monomers, photo-active polymers, photo-activeoligomers and/or photo-active monomers, depending upon the applicationto which the polymer or oligomer layer is to be added. Therefore it isunderstood that by varying the composition of the polymer or oligomerlayer it is possible to control specific and desired properties, such asan induced pre-tilt angle, good surface wetting, a high voltage holdingratio, a specific anchoring energy, etc.

Polymer or oligomer layers may readily be prepared from the polymers oroligomers of the present invention and a further embodiment of theinvention relates to a polymer or oligomer layer comprising a polymer oroligomer according to the present invention, which is preferablyprepared by treatment with aligning light. Preferably, the inventionrelates to a polymer or oligomer layer comprising a polymer or oligomeraccording to the present invention in a cross-linked and/or isomerizedform.

The polymer or oligomer layer is preferably prepared by applying one ormore polymers or oligomers according to the invention to a support and,after imidisation or without imidisation, treating, preferablycross-linking and/or isomerising, the polymer or oligomer or polymermixture or oligomer mixture by irradiation with aligning light.

In general, transparent support such as glass or plastic substrates,optionally coated with indium tin oxide (ITO) are used.

Further, it is possible to vary the direction of orientation and thetilt angle within the polymer or oligomer layer by controlling thedirection of the irradiation of the aligning light. It is understoodthat by selectively irradiating specific regions of the polymer oroligomer layer very specific regions of the layer can be aligned. Inthis way, layers with a defined tilt angle can be provided. The inducedorientation and tilt angle are retained in the polymer or oligomer layerby the process, especially by the process of cross-linking.

Method for the preparation of a polymer, copolymer or oligomer accordingto the invention, wherein in a polycondensation reaction a diamine (I)is reacted with one or more tetracarboxylic acid anhydrides of thegeneral formula (V), optionally in the presence of one or moreadditional other diamines.

Further, the present invention preferably concerns a method, wherein apolycondensation reaction for the preparation of the polyamic acids iscarried out in solution in a polar aprotic organic solvent, preferablyselected from γ-butyrolactone, N,N-dimethylacetamide,N-methylpyrrolidone or N,N-dimethylformamide.

Preferably, the present invention concerns a method, wherein subsequentto the polycondensation cyclisation with removal of water is carried outthermally under formation of a polyimide.

More preferably, the present invention concerns a method, whereinimidisation is carried out prior or after the application of thepolymer, copolymer or oligomer to a support.

Further preferred methods of the invention relates to

-   -   a method for the preparation of a polymer layer or oligomer        layer, which are vertically aligned;    -   a method for the preparation of multi-domain vertical alignment        of a polymer layer or oligomer layer;    -   a method for the preparation of a polymer layer or oligomer        layer with tilted optical axis.

A further embodiment of the present invention concerns a polymer,copolymer or oligomer layer, in particular orientation layer, comprisingat least one polymer, copolymer or oligomer according to the presentinvention.

It is understood that the polymer or oligomer layers of the presentinvention (in form of a polymer gel, a polymer network, a polymer film,etc.) can also be used as orientation layers for liquid crystals. Afurther preferred embodiment of the invention relates to an orientationlayer comprising one or more polymers or oligomers according to theinvention, preferably in a cross-linked form. Such orientation layerscan be used in the manufacture of unstructured or structured optical- orelectro-optical elements, preferably in the production of hybrid layerelements.

In addition, the present invention concerns a method for the preparationof a polymer layer or oligomer layer, wherein one or more polymers,copolymers or oligomers according to the present invention is applied toa support, preferably from a solution of the polymer or oligomermaterial and subsequent evaporation of the solvent, and wherein, afterany imidisation step which may be necessary, the polymer or oligomer orpolymer mixture or oligomer mixture treated with aligning light, andpreferably isomerized and/or cross-linked by irradiation with aligninglight.

A preferred method of the present invention concerns a method, whereinthe direction of orientation and the tilt angle within the polymer layeror oligomer layer is varied by controlling the direction of theirradiation with aligning light, and/or wherein by selectivelyirradiating specific regions of the polymer layer or oligomer layerspecific regions of the layer are aligned.

The orientation layers are suitably prepared from a solution of thepolymer or oligomer material. The polymer or oligomer solution isapplied to a support optionally coated with an electrode [for example aglass plate coated with indium-tin oxide (ITO)] so that homogeneouslayers of 0.05 to 50 μm thickness are produced. In this processdifferent coating techniques like spin-coating, meniscus-coating,wire-coating, slot-coating, offset-printing, flexo-printing,gravur-printing may be used. Then, or optionally after a priorimidisation step, the regions to be oriented are irradiated, forexample, with a high-pressure mercury vapour lamp, a xenon lamp or apulsed UV laser, using a polarizer and optionally a mask for creatingimages of structures.

Further, the present invention concerns the use of a polymer layer,copolymer or oligomer layer according to the present invention,preferably in cross-linked form, as an orientation layer for liquidcrystals.

Further, the present invention concerns preferably the use of a polymerlayer, copolymer or oligomer layer for the induction of verticalalignment of adjacent liquid crystalline layers, in particular foroperating a cell in MVA mode.

The irradiation time is dependent upon the output of the individuallamps and can vary from a few seconds to several hours. Thephoto-reaction (dimerisation, polymersiation, cross-linking) can also becarried out, however, by irradiation of the homogeneous layer usingfilters that, for example, allow only the radiation suitable for thecross-linking reaction to pass through.

It is understood that the polymer or oligomer layers of the inventionmay be used in the production of optical or electro-optical deviceshaving at least one orientation layer as well as unstructured andstructured optical elements and multi-layer systems.

The present invention concerns the use of a polymer layer, copolymer oroligomer layer as an orientation layer for liquid crystals.

Preferred is the use for the induction of vertical alignment of adjacentliquid crystalline layers.

A further embodiment of the invention relates to an optical orelectro-optical device comprising one or more polymers or oligomersaccording to the present invention in cross-linked form. Theelectro-optical devices may comprise more than one layer. The layer, oreach of the layers may contain one or more regions of different spatialorientation.

Preferably, the present invention concerns an optical andelectro-optical unstructured or structured constructional elements,preferably liquid crystal display cells, multi-layer and hybrid layerelements, comprising at least one polymer layer, copolymer or oligomerlayer according to the present invention.

More preferably, the present invention concerns an orientation layer,comprising at least one polymer layer, copolymer or oligomer layeraccording to the present invention.

The advantages of the present invention could not be foreseen by askilled person. It has surprisingly been found, that in addition to thepolyamic/polyimide backbone, the introduction of an organofluorine groupinto a peripheral position of the polymer side groups having specificmolecular architecture plays a predominant role in obtaining MVAmaterials having optimised properties, such as the required high voltageholding ratios, the adjustable pre-tilt angles required for the MVA modeand their stability to light and heat.

EXAMPLE 1 Synthesis Preparation of(2E)-3-(4-{[4-(4,4,4-trifluorobutoxy)benzoyl]oxy}phenyl)acrylic acid 1.1Preparation of 4-(4,4,4-trifluorobutoxy)benzoic acid

55.00 g (0.408 Mol) 4,4,4-trifluorobutan-1-ol arre dissolved in 550 mltetrahydrofurane, 142 ml (0.102 Mol) triethylamine are added at roomtemperature 38 ml (0.490 Mol) methanesulfonyl chloride were addeddropwise under nitrogen. The mixture is stirred for 1 h at 0-5° C. Thebeige suspension is Hyflo-filtrated and washed with tetrahydrofurane.The filtrate is concentrated. The residue is dissolved in 1.4 l1-methyl-2-pyrrolidone 62.70 g (0.408 Mol) of methyl 4-hydroxybenzoateand 226.00 g (1.43 Mol) of potassium carbonate are added to the lightlybrown solution. The reaction suspension is allowed to react at 80° C.for 14 h. 1 l (1.0 Mol) of a 1N NaOH solution is added to the abovemixture. The suspension is heated at reflux temperature for 30 min untilthe reaction is completed. The reaction mixture is allowed to cool atroom temperature and thrown in cold water. The solution is carefullyacidified with a 25% HCl solution and is stirred for 15 min. The productis filtrated off, washed with water and dried overnight at roomtemperature under vacuum to give 99.00 g (98%) of4-(4,4,4-trifluorobutoxy)benzoic acid as a white solid.

1.2 Preparation of 4-Formylphenyl-4-(4,4,4-trifluorobutoxy)benzoate

6.89 g (56.4 mmol) of 4-hydroxybenzaldehyd, 14.0 g (56.4 mmol) of4-(4,4,4-trifluorobutoxy)benzoic acid, 0.69 g (5.6 mmol) of4-Dimethylaminopyridine are dissolved in 100 ml of dichloromethane.11.89 g (62.0 mmol) of N-(3-Dimethylaminopropyl)-N′-ethylcarbodiimidehydrochloride (EDC hydrochloride) are added at 0° C. The solution isstirred for 1 h at 0° C. and allowed to stir at room temperatureovernight. After 22 hours at room temperature the reaction mixture waspartitioned between dichloromethane and water; the organic phase iswashed repeatedly with water, dried over sodium sulphate, filtered andconcentrated by rotary evaporation. Crystallization form 2-propanol at0° C. give 17.1 g 4-formylphenyl-4-(4,4,4-trifluorobutoxy)benzoate ascolourless crystals.

1.3 Preparation of(2E)-3-(4-{[4-(4,4,4-trifluorobutoxy)benzoyl]oxy}phenyl)acrylic acid

5.00 g (14.2 mMol) of 4-formylphenyl 4-(4,4,4-trifluorobutoxy)benzoateand 3.00 g (28.4 mMol) of Malonic acid are dissolved in 18 ml (227.1mMol) of Pyridin. 1.21 g (14.2 mMol) of Piperidin are added to thesuspension which is allowed to react at 100° C. under argon for 1.5 h.The yellow solution is then thrown on ice. The solution is carefullyacidified to pH=1-2 with a 25% HCl solution and is stirred for 15 min.The product is filtrated off and dried at room temperature under vacuumfor 10 h to give 5.2 g of(2E)-3-(4-{[4-(4,4,4-trifluorobutoxy)benzoyl]oxy}phenyl)acrylic acid aswhite powder.

(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}acrylicacid is prepared analogous to example 1 using4,4,5,5,5-pentafluoropentan-1-ol instead of 4,4,4-trifluorobutan-1-ol.

The following acrylic acid are synthesized in an analogous manner:

-   (2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}acrylic acid-   (2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}acrylic acid-   (2E)3-{4-[(4-(2,2,2-trifluoropropoxy)benzoyl)oxy]phenyl}acrylic acid-   (2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}acrylic    acid-   (2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylic    acid-   (2E)3-{4-[(4-(1,1,2,2-tetrafluoropropoxy)benzoyl)oxy]phenyl}acrylic    acid-   (2E)3-{4-[(4-(4,4,5,5,6,6,6-heptafluorohexyloxy)benzoyl)oxy]phenyl}acrylic    acid

EXAMPLE 2 Synthesis Preparation of6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl3,5-diaminobenzoate 2.1 Preparation of(2E)-3-{4-[(ethoxycarbonyl)oxy]phenyl}acrylic acid

67 g (0.41 mol) p-cumaric acid are added to a mixture of 50.4 g (0.90mol) potassium hydroxide and 600 ml water. 53.1 g (0.50 mol) ethylchloroformate are added dropwise at 0° C. The reaction temperature risesto 10° C. The reaction mixture is subsequently allowed to react for 2hours at 25° C. and acidified to pH=1 with 200 ml hydrochloric acid 7N.The product is filtered off, washed with water and dried under vacuum togive 95.3 g of (2E)-3-{4-[(ethoxycarbonyl)oxy]phenyl}acrylic acid aswhite powder.

2.2 Preparation of 6-hydroxyhexyl 3,5-dinitrobenzoate

357.70 g (1.686 Mol) of 3,5-dinitrobenzoic acid are suspended in 750 mlof 1-methyl-2-pyrrolidone. The suspension is stirred up to 50° C. 386.36g (4.599 Mol) of sodium hydrogen carbonate are added and the mixture washeated up to 90° C. 22.50 g (0.150 Mol) of sodium iodide and 204.0 ml(1.533 Mol) of 6-chlorohexanol are added to the reaction mixture whichis heated to 100° C. for 1 h. After 1 h of reaction, the reaction iscomplete and the orange suspension is thrown on 2 l of ice and 1 l ofwater. The product is filtrated, washed water and dried at 50° C. undervacuum for 24 h to give 425.0 g (91%) of 6-hydroxyhexyl3,5-dinitrobenzoate as a rose powder.

2.3 Preparation of6-[((2E)-{4-[(ethoxycarbonyl)oxy]phenyl}prop-2-enoyl)oxy]hexyl3,5-dinitrobenzoate

4.53 g (0.0145 Mol) of 6-hydroxyhexyl 3,5-dinitrobenzoate, 3.44 g(0.0145 Mol) of 4-ethylcarbonatecinnamic acid, 0.177 g (0.0015 Mol) of4-Dimethylaminopyridine are dissolved in 40 ml of dichloromethane. 3.04g (0.0159 Mol) of N-(3-Dimethylaminopropyl)-N′-ethylcarbodiimidehydrochloride (EDC hydrochloride) are added at 0° C. The solution isstirred for 1 h at 0° C. and allowed to stir at room temperatureovernight. After 22 hours at room temperature the reaction mixture ispartitioned between dichloromethane and water; the organic phase iswashed repeatedly with water, dried over sodium sulphate, filtered andconcentrated by rotary evaporation. The residue is dissolved ethylacetate. The product is precipitated with Hexane at 0° C. Theprecipitated is filtrated and dried under vacuum overnight to give 4.2 g(55%) of 6-[((2E)-{4-[(ethoxycarbonyl)oxy]phenyl}prop-2-enoyl)oxy]hexyl3,5-dinitrobenzoate as a light-yellow powder.

2.4 Preparation of 6-[((2E)-{4-hydroxyphenyl}prop-2-enoyl)oxy]hexyl3,5-dinitrobenzoate

43.20 g (0.081 Mol) of6-[((2E)-{4-[(ethoxycarbonyl)oxy]phenyl}prop-2-enoyl)oxy]hexyl3,5-dinitrobenzoate are dissolved in 66 ml (0.815 Mol) of pyridine and400 ml of acetone at room temperature. 61 ml (0.815 Mol) of ammoniumhydroxide solution 25% are added dropwise to the solution at roomtemperature. After 12 h reaction, the mixture is thrown on water andacidified by the addition of HCl 25% (up to pH=3-4). A paste is obtainedwhich is filtrated and dissolved in ethyl acetate and extracted withwater. The organic phase is dried with sodium sulfate, filtrated,concentrated by rotary evaporation. Filtration of the residue oversilica gel with tert-Butyl methyl ether as eluant and crystallization ofthe residue in 200 ml of ethyl acetate and 1200 ml of hexane at 0° C.give 15.84 g of 6-[((2E)-{4-hydroxyphenyl}prop-2-enoyl)oxy]hexyl3,5-dinitrobenzoate as yellow crystals.

2.5 Preparation of6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl3,5-dinitrobenzoate

8.61 g (0.0347 Mol) of 4-(4,4,4-trifluorobutoxy)benzoic acid aresuspended in 100 ml of dichloromethane. 0.42 g (0.0035 Mol) of4-Dimethylaminopyridine are added at room temperature. 7.98 g (0.04163Mol) of N-(3-Dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride(EDC hydrochloride) are added at 0° C. The solution is stirred for 1 hat 0° C. 15.90 g (0.0347 Mol) of6-[((2E)-{4-hydroxyphenyl}prop-2-enoyl)oxy]hexyl 3,5-dinitrobenzoatedissolved in 50 ml of dichloromethane are added dropwise to the solutionat 0° C. and allowed to stir at room temperature overnight. After 22hours at room temperature the reaction mixture is partitioned betweendichloromethane and water. The mixture is acidified with HCl 25%. Theorganic phase is washed repeatedly with water, dried over sodiumsulphate, filtered and concentrated by rotary evaporation.Chromatography of the residue on 600 g silica gel using toluene:ethylacetate (99:1) as eluant and crystallization from ethyl acetate/hexane(1:2) yielded 18.82 g (79%) of6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl3,5-dinitrobenzoate as white crystals.

2.6 Preparation of6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl3,5-diaminobenzoate

18.80 g (0.027 Mol) of6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl3,5-dinitrobenzoate are dissolved in a mixture of 350 ml ofN,N-dimethylformamide and 25 ml water. 44.28 g (0.164 Mol) ferricchloride hexahydrate are added. 17.85 g (0.273 Mol) Zinc powder areadded portionwise within 40 min. The mixture is allowed to react for 2hours. The reaction mixture is then partitioned between ethyl acetateand water and filtered. The organic phase is washed repeatedly withwater, dried over sodium sulfate, filtered and concentrated by rotaryevaporation. Chromatography of the residue on 400 g silica gel usingtoluene:ethyl acetate (2:1) as eluant yielded 15.39 g (91%) of6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl3,5-diaminobenzoate as yellowish crystals.

The following diamines are synthesized in an analogous manner:

-   2-{[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl    3,5-diaminobenzoate.-   3-{[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl    3,5-diaminobenzoate.-   4-{[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl    3,5-diaminobenzoate.-   5-{[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}pentyl    3,5-diaminobenzoate-   7-{[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}heptyl    3,5-diaminobenzoate.-   8-{[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl    3,5-diaminobenzoate.-   11-{[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}undecyl    3,5-diaminobenzoate.-   2-{[((2E)-3-{4-[(4-(trifluoromethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl    3,5-diaminobenzoate.-   3-{[((2E)-3-{4-[(4-(trifluoromethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl    3,5-diaminobenzoate.-   4-{[((2E)-3-{4-[(4-(trifluoromethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl    3,5-diaminobenzoate.-   5-{[((2E)-3-{4-[(4-(trifluoromethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}pentyl    3,5-diaminobenzoate-   6-{[((2E)-3-{4-[(4-(trifluoromethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyll    3,5-diaminobenzoate-   7-{[((2E)-3-{4-[(4-(trifluoromethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}heptyl    3,5-diaminobenzoate.-   8-{[((2E)-3-{4-[(4-(trifluoromethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl    3,5-diaminobenzoate.-   2-{[((2E)-3-{4-[(4-(trifluoromethyl)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl    3,5-diaminobenzoate.-   3-{[((2E)-3-{4-[(4-(trifluoromethyl)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl    3,5-diaminobenzoate.-   4-{[((2E)-3-{4-[(4-(trifluoromethyl)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl    3,5-diaminobenzoate.-   5-{[((2E)-3-{4-[(4-(trifluoromethyl)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}pentyl    3,5-diaminobenzoate-   6-{[((2E)-3-{4-[(4-(trifluoromethyl)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyll    3,5-diaminobenzoate-   8-{[((2E)-3-{4-[(4-(trifluoromethyl)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl    3,5-diaminobenzoate-   11-{[((2E)-3-{4-[(4-(trifluoromethyl)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}undecyll    3,5-diaminobenzoate-   2-[2-{[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethyl    3,5-diaminobenzoate-   2{2-[2-{[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethoxy}ethyl    3,5-diaminobenzoate-   2,2-dimethyl-3-{[((2E)-3-{4-[(4-(trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl    3,5-diaminobenzoate-   2-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl    3,5-diaminobenzoate-   3-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl    3,5-diaminobenzoate-   4-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl    3,5-diaminobenzoate.-   6-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl    3,5-diaminobenzoate-   7-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}heptyl    3,5-diaminobenzoate-   8-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl    3,5-diaminobenzoate-   11-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}undecyl    3,5-diaminobenzoate-   2-[2-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethyl    3,5-diaminobenzoate-   2{2-[2-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethoxy}ethyl    3,5-diaminobenzoate-   2,2-dimethyl-3-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl    3,5-diaminobenzoate-   2-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl    3,5-diaminobenzoate-   3-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl    3,5-diaminobenzoate.-   4-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl    3,5-diaminobenzoate.-   5-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}pentyl    3,5-diaminobenzoate-   7-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}heptyl    3,5-diaminobenzoate.-   8-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl    3,5-diaminobenzoate.-   11-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}undecyl    3,5-diaminobenzoate.-   2-[2-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethyl    3,5-diaminobenzoate-   2{2-[2-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethoxy}ethyl    3,5-diaminobenzoate-   2,2-dimethyl-3-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl    3,5-diaminobenzoate-   2-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl    3,5-diaminobenzoate-   3-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl    3,5-diaminobenzoate-   4-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl    3,5-diaminobenzoate-   5-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}pentyl    3,5-diaminobenzoate-   6-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl    3,5-diaminobenzoate-   8-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl    3,5-diaminobenzoate-   11-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}undecyl    3,5-diaminobenzoate-   2-[2-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethyl    3,5-diaminobenzoate-   2{2-[2-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethoxy}ethyl    3,5-diaminobenzoate-   2,2-dimethyl-3-{[((2E)-3-{4-[(4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl    3,5-diaminobenzoate-   2-{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl    3,5-diaminobenzoate-   3-{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl    3,5-diaminobenzoate-   4-{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl    3,5-diaminobenzoate-   5-{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}pentyl    3,5-diaminobenzoate-   7-{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}heptyl    3,5-diaminobenzoate-   8-{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl    3,5-diaminobenzoate-   11-{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}undecyl    3,5-diaminobenzoate-   2-[2-{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethyl    3,5-diaminobenzoate-   2{2-[2-{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethoxy}ethyl    3,5-diaminobenzoate-   2,2-dimethyl-3-{[((2E)-3-{4-[(4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl    3,5-diaminobenzoate-   3-{[((2E)-3-{4-[(3-methoxy    4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl    3,5-diaminobenzoate-   8-{[((2E)-3-{4-[(3-methoxy    4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl    3,5-diaminobenzoate-   11-{[((2E)-3-{4-[(3-methoxy    4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}undecyl    3,5-diaminobenzoate-   6-{[((2E)-3-{4-[(3-methoxy    4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyll    3,5-diaminobenzoate-   8-{[((2E)-3-{4-[(3-methoxy    4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl    3,5-diaminobenzoate-   11-{[((2E)-3-{4-[(3-methoxy    4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}undecyl    3,5-diaminobenzoate-   4-{[((2E)-3-{4-[(3-methoxy    4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl    3,5-diaminobenzoate-   6-{[((2E)-3-{4-[(3-methoxy    4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl3,5-diaminobenzoate-   4-{[((2E)-3-{4-[(3-methoxy    4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl    3,5-diaminobenzoate-   6-{[((2E)-3-{4-[(3-methoxy    4-(6,6,6-trifluorohexyloxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl    3,5-diaminobenzoate-   2-{[((2E)-3-{4-[(4-(4, 4, 5, 5,    5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl    3,5-diaminobenzoate-   3-{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl    3,5-diaminobenzoate-   4-{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl    3,5-diaminobenzoate-   6-{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl    3,5-diaminobenzoate-   7-{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}heptyl    3,5-diaminobenzoate-   8-{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl    3,5-diaminobenzoate-   11-{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}undecyl    3,5-diaminobenzoate-   2-[2-{[((2E)-3-{4-[(4-(4, 4, 5, 5,    5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethyl    3,5-diaminobenzoate-   2{2-[2-{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethoxy}ethyl    3,5-diaminobenzoate-   2,2-Dimethyl-3-{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl    3,5-diaminobenzoate-   2-{[((2E)-3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl    3,5-diaminobenzoate-   3-{[((2E)-3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl    3,5-diaminobenzoate-   4-{[((2E)-3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl    3,5-diaminobenzoate-   5-{[((2E)-3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}pentyl    3,5-diaminobenzoate-   6-{[((2E)-3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyll    3,5-diaminobenzoate-   7-{[((2E)-3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}heptyl    3,5-diaminobenzoate.-   8-{[((2E)-3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl    3,5-diaminobenzoate-   11-{[((2E)-3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}undecyl    3,5-diaminobenzoate-   6-{[((2E)-3-{4-[(4-{[(4,4,4-trifluorobutoxy)carbonyl]amino}benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyll    3,5-diaminobenzoate-   6-{[((2E)-3-{4-[(4-{[(4,4,5,5,5-pentafluoropentoxy)carbonyl]amino}benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyll    3,5-diaminobenzoate-   6-{[((2E)-3-{4-[(4-({[(4,4,5,5,6,6,6-heptafluorohexyloxy)carbonyl]amino})benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyll    3,5-diaminobenzoate

EXAMPLE 3 Synthesis Preparation of 3,5-Diaminobenzyl(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate 3.1Preparation of 3,5-dinitrobenzyl(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate

1.00 g (51.0 mmol) of 3,5-dinitrobenzylalcohol, 2.00 g (51.0 mmol) of(2E)-3-(4-{[4-(4,4,4-trifluorobutoxy)benzoyl]oxy}phenyl)acrylic acid, 62mg (0.51 mmol) of 4-Dimethylaminopyridine are dissolved in 10 ml ofdichloromethane. 1.07 g (56.0 mmol) ofN-(3-Dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (EDChydrochloride) are added at 0° C. The solution is stirred for 1 h at 0°C. and allowed to stir at room temperature overnight. After 22 hours atroom temperature the reaction mixture is partitioned betweendichloromethane and water. The organic phase is washed repeatedly withwater, dried over sodium sulphate, filtered and concentrated by rotaryevaporation to yield 3,5-dinitrobenzyl(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate 2.1 g ascolorless crystals.

3.2 Preparation of 3,5-Diaminobenzyl(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate

5.30 g (9.22 mmol) of(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate aredissolved in a mixture of 55 ml of N,N-dimethylformamide and 6 ml water.14.98 g (55.3 mmol) ferric chloride hexahydrate are added. 6.03 g (91.8mmol) Zinc powder are added portionwise within 40 min. The mixture isallowed to react for 2 hours. The reaction mixture is then partitionedbetween ethyl acetate and water and filtered. The organic phase iswashed repeatedly with water, dried over sodium sulfate, filtered andconcentrated by rotary evaporation. Chromatography of the residue on 200g silica gel using toluene:ethyl acetate (1:1) as eluant andcrystallization form ethylacetate:hexane mixture yielded 3.8 g3,5-Diaminobenzyl(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate asyellowish crystals

The following diamines are synthesized in an analogous manner:

-   3,5-Diaminobenzyl    (2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}acrylate-   3,5-Diaminobenzyl    (2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}acrylate-   3,5-Diaminobenzyl    (2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}acrylate-   3,5-Diaminobenzyl    (2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}acrylate-   3,5-Diaminobenzyl    (2E)3-{4-[(4-(3,3,4,4,5,5,6,6,6-nonafluorohexyloxy)benzoyl)oxy]phenyl}acrylate-   3,5-Diaminobenzyl    (2E)3-{4-[(4-(2,2,3,3,3-pentafluoropropyloxy)benzoyl)oxy]phenyl}acrylate-   3,5-Diaminobenzyl    (2E)3-{4-[(4-(2,2,3,4,4,4-hexafluorobutoxy)benzoyl)oxy]phenyl}acrylate-   3,5-Diaminobenzyl    (2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylate-   3,5-Diaminobenzyl    (2E)3-{4-[(4-(1,1,2,2-tetrafluoropropoxy)benzoyl)oxy]phenyl}acrylate-   3,5-Diaminobenzyl (2E)3-{4-[(4-(4, 4, 5, 5, 6, 6,    6-heptafluorohexyloxy)benzoyl)oxy]phenyl}acrylate-   3,5-Diaminobenzyl    (2E)3-{4-[(4-(4,5,5,5-tetrafluoro-4-(trifluoromethyl)pentyloxy)benzoyl)oxy]phenyl}acrylate-   3,5-Diaminobenzyl    (2E)3-{4-{[(4-(4,4,5,5,6,6,6-heptafluorohexyloyl)oxy)benzoyl    oxy]phenyl}acrylate-   3,5-Diaminobenzyl    (2E)3-{4-[(4-[(4,4,4-trifluorobutoxy)carbonyl]amino)benzoyl)oxy]phenyl}acrylate-   3,5-Diaminobenzyl    (2E)3-{4-[(4-[(4,4,4-trifluoropentyloxy)carbonyl]amino)    benzoyl]oxy}phenyl}acrylate-   3,5-Diaminobenzyl    (2E)3-{4-[4-(4,4,5,5,5-pentafluoropentyloyloxy)benzoyl    oxy]phenyl}acrylate-   3,5-Diaminobenzyl    (2E)3-{4-[4-(4,4,5,5,6,6,6-heptafluorohexyloyloxy)benzoyl    oxy]phenyl}acrylate-   3,5-Diaminobenzyl    (2E)3-{4-[(3-fluoro-4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate-   2,5-Diaminobenzyl    (2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}acrylate-   2,5-Diaminobenzyl    (2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}acrylate-   2,5-Diaminobenzyl    (2E)3-{4-[(4-(5,5,5-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate-   2,5-Diaminobenzyl    (2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}acrylate-   2,5-Diaminobenzyl    (2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}acrylate-   2,5-Diaminobenzyl    (2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylate-   2,5-Diaminobenzyl    (2E)3-{4-[(4-(1,1,2,2-tetrafluoropropoxy)benzoyl)oxy]phenyl}acrylate-   2,5-Diaminobenzyl    (2E)3-{4-[(4-(4,4,5,5,6,6,6-heptafluorohexyloxy)benzoyl)oxy]phenyl}acrylate-   2,5-Diaminobenzyl (2E)3-{4-{[(4-(4, 4, 5, 5, 6, 6,    6-heptafluorohexyloyl)oxy)benzoyl oxy]phenyl}acrylate-   2,5-Diaminobenzyl    (2E)3-{4-[(4-[(4,4,4-trifluorobutoxy)carbonyl]amino)benzoyl)oxy]phenyl}acrylate-   2,5-Diaminobenzyl    (2E)3-{4-[(4-[(4,4,4-trifluoropentyloxy)carbonyl]amino)    benzoyl]oxy}phenyl}acrylate-   2,5-Diaminobenzyl    (2E)3-{4-[4-(4,4,5,5,5-pentafluoropentyloyloxy)benzoyl    oxy]phenyl}acrylate-   2,5-Diaminobenzyl    (2E)3-{4-[4-(4,4,5,5,6,6,6-heptafluorohexyloyloxy)benzoyl    oxy]phenyl}acrylate2,5-Diaminobenzyl    (2E)3-{4-[(2-fluoro-4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate-   2,4-Diaminobenzyl    (2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}acrylate-   2,4-Diaminobenzyl    (2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}acrylate-   2,4-Diaminobenzyl    (2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}acrylate-   2,4-Diaminobenzyl    (2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate-   2,4-Diaminobenzyl    (2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}acrylate-   2,4-Diaminobenzyl    (2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylate-   2,4-Diaminobenzyl    (2E)3-{4-[(4-(1,1,2,2-tetrafluoropropoxy)benzoyl)oxy]phenyl}acrylate-   2,4-Diaminobenzyl    (2E)3-{4-[(4-(4,4,5,5,6,6,6-heptafluorohexyloxy)benzoyl)oxy]phenyl}acrylate-   2,4-Diaminobenzyl    (2E)3-{4-{[(4-(4,4,5,5,6,6,6-heptafluorohexyloyl)oxy)benzoyl    oxy]phenyl}acrylate-   2,4-Diaminobenzyl    (2E)3-{4-[(4-[(4,4,4-trifluorobutoxy)carbonyl]amino)benzoyl)oxy]phenyl}acrylate-   2,4-Diaminobenzyl    (2E)3-{4-[(4-[(4,4,4-trifluoropentyloxy)carbonyl]amino)    benzoyl]oxy}phenyl}acrylate-   2,4-Diaminobenzyl (2E)3-{4-[4-(4, 4, 5, 5,    5-pentafluoropentyloyloxy)benzoyl oxy]phenyl}acrylate-   2,4-Diaminobenzyl    (2E)3-{4-[4-(4,4,5,5,6,6,6-heptafluorohexyloyloxy)benzoyl    oxy]phenyl}acrylate-   2,4-Diaminobenzyl    (2E)3-{4-[(3-fluoro-4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate

EXAMPLE 4 Synthesis Preparation of 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}acrylate4.1 Preparation of 2-(2,4-dinitrophenyl)ethanol

22.6 g (100 mmol) 2,4-dinitrophenylacetic acid are dissolved in 150 mltetrahydrofuran and added dropwise in a the course of 2 hours to 300 ml(300 mmol) of a borane-tetrahydrofuran complex 1.0 M solution intetrahydrofuran. After 3 hours at 25° C., 200 ml water are carefullyadded. The reaction mixture is then partitioned between ethyl acetateand water; the organic phase was washed repeatedly with water, driedover sodium sulfate, filtered and concentrated by rotary evaporation.Chromatography of the residue on 400 g silica gel using toluene:ethylacetate 1:1 as eluant and crystallization form ethylacetate:hexanemixture to yield 20.7 g (98%) of 2-(2,4-dinitrophenyl)ethanol asyellowish crystals.

4.2 Preparation of 2-(2,4-Dinitrophenyl)ethyl(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}acrylate

2.50 g (11.8 mmol) of 2-(2,4-dinitrophenyl)ethanol, 5.24 g (11.8 mmol)of(2E)-3-(4-{[4-(4,4,5,5,5-pentafluoropentoxy)benzoyl]oxy}phenyl)acrylicacid, 144 mg (1.2 mmol) of 4-Dimethylaminopyridine are dissolved in 30ml of dichloromethane. 2.48 g (13.0 mmol) ofN-(3-Dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (EDChydrochloride) are added at 0° C. The solution is stirred for 1 h at 0°C. and allowed to stir at room temperature overnight. After 22 hours atroom temperature the reaction mixture is partitioned betweendichloromethane and water. The organic phase is washed repeatedly withwater, dried over sodium sulphate, filtered and concentrated by rotaryevaporation. Chromatography of the residue on 200 g silica gel usingtoluene:ethyl acetate 95:5 as eluant and crystallization formethylacetate:hexane mixture to yield 5.35 g (71%)2-(2,4-Dinitrophenyl)ethyl(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}acrylateas colorless crystals.

4.3 Preparation of 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}acrylate

5.35 g (8.38 mmol) of(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}acrylateare dissolved in a mixture of 54 ml of N,N-dimethylformamide and 6 mlwater. 13.9 g (51.4 mmol) ferric chloride hexahydrate are added. 5.60 g(85.7 mmol) Zinc powder are added portionwise within 60 min. The mixtureis allowed to react for 2 hours. The reaction mixture is thenpartitioned between ethyl acetate and water and filtered. The organicphase is washed repeatedly with water, dried over sodium sulfate,filtered and concentrated by rotary evaporation. Filtration of theresidue on 200 g silica gel using toluene:ethyl acetate (1:3) as eluantand crystallization form ethylacetate:hexane mixture yielded 3.30 g2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}acrylateas yellowish crystals 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate isprepared analogous to example 4 using(2E)-3-(4-{[4-(4,4,4-trifluorobutoxy)benzoyl]oxy}phenyl)acrylic acid.

The following diamines are synthesized in an analogous manner:

-   2-(3,5-Diaminophenyl)ethyl    (2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}acrylate-   2-(3,5-Diaminophenyl)ethyl    (2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}acrylate-   2-(3,5-Diaminophenyl)ethyl    (2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate-   2-(3,5-Diaminophenyl)ethyl    (2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}acrylate-   2-(3,5-Diaminophenyl)ethyl    (2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}acrylate-   2-(3,5-Diaminophenyl)ethyl    (2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylate-   2-(3,5-Diaminophenyl)ethyl    (2E)3-{4-[(4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxy}phenyl}acrylate-   2-(3,5-Diaminophenyl)ethyl    (2E)3-{4-[(3-methoxy-4-trifluoromethoxybenzoyl)oxy]phenyl}acrylate-   2-(3,5-Diaminophenyl)ethyl (2E)3-{4-[(3-methoxy    4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}acrylate-   2-(3,5-Diaminophenyl)ethyl (2E)3-{4-[(3-methoxy    4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate-   2-(3,5-Diaminophenyl)ethyl (2E)3-{4-[(3-methoxy    4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}acrylate-   2-(3,5-Diaminophenyl)ethyl (2E)3-{4-[(3-methoxy    4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}acrylate-   2-(3,5-Diaminophenyl)ethyl (2E)3-{4-[(3-methoxy    4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylate-   2-(3,5-Diaminophenyl)ethyl (2E)3-{4-[(3-methoxy    4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxy}phenyl}acrylate-   2-(3,5-Diaminophenyl)ethyl    (2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]-3-methoxyphenyl}acrylate-   2-(3,5-Diaminophenyl)ethyl    (2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]-3-methoxyphenyl}acrylate-   2-(3,5-Diaminophenyl)ethyl    (2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]-3-methoxyphenyl}acrylate-   2-(3,5-Diaminophenyl)ethyl    (2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]-3-methoxyphenyl}acrylate-   2-(3,5-Diaminophenyl)ethyl    (2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]-3-methoxyphenyl}acrylate-   2-(3,5-Diaminophenyl)ethyl    (2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]-3-methoxyphenyl}acrylate-   2-(3,5-Diaminophenyl)ethyl    (2E)3-{4-[(4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxy}-3-methoxyphenyl}acrylate-   2-(3,5-Diaminophenyl)ethyl    (2E)3-{4-[(4-trifluoromethoxyphenoxy)carbonyl]phenyl}acrylate-   2-(3,5-Diaminophenyl)ethyl    (2E)3-{4-[(4-(2,2,2-trifluoroethoxy)phenoxy)carbonyl]phenyl}acrylate-   2-(3,5-Diaminophenyl)ethyl    (2E)3-{4-[(4-(4,4,4-trifluorobutoxy)phenoxy)carbonyl]phenyl}acrylate-   2-(3,5-Diaminophenyl)ethyl    (2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)phenoxy)carbonyl]phenyl}acrylate-   2-(3,5-Diaminophenyl)ethyl    (2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)phenoxy)carbonyl]phenyl}acrylate-   2-(3,5-Diaminophenyl)ethyl    (2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)phenoxy)carbonyl]phenyl}acrylate-   2-(2,5-Diaminophenyl)ethyl    (2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}acrylate-   2-(2,5-Diaminophenyl)ethyl    (2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}acrylate-   2-(2,5-Diaminophenyl)ethyl    (2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate-   2-(2,5-Diaminophenyl)ethyl    (2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}acrylate-   2-(2,5-Diaminophenyl)ethyl (2E)3-{4-[(4-(4, 4, 5, 5,    5-pentafluoropentoxy)benzoyl)oxy]phenyl}acrylate-   2-(2,5-Diaminophenyl)ethyl    (2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylate-   2-(2,5-Diaminophenyl)ethyl    (2E)3-{4-[(4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxy]phenyl}acrylate-   2-(2,4-Diaminophenyl)ethyl    (2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}acrylate-   2-(2,4-Diaminophenyl)ethyl    (2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}acrylate-   2-(2,4-Diaminophenyl)ethyl    (2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate-   2-(2,4-Diaminophenyl)ethyl    (2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}acrylate-   2-(2,4-Diaminophenyl)ethyl    (2E)3-{4-[(4-(2,2,3,3,3-pentafluoropropyloxy)benzoyl)oxy]phenyl}acrylate-   2-(2,4-Diaminophenyl)ethyl    (2E)3-{4-[(4-(2,2,3,4,4,4-hexafluorobutoxy)benzoyl)oxy]phenyl}acrylate-   2-(2,4-Diaminophenyl)ethyl    (2E)3-{4-[(4-(3,3,4,4,5,5,6,6,6-nonafluorohexyloxy)benzoyl)oxy]phenyl}acrylate-   2-(2,4-Diaminophenyl)ethyl    (2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylate-   2-(2,4-Diaminophenyl)ethyl    (2E)3-{4-[(4-(1,1,2,2-tetrafluoropropoxy)benzoyl)oxy]phenyl}acrylate-   2-(2,4-Diaminophenyl)ethyl    (2E)3-{4-[(4-(4,4,5,5,6,6,6-heptafluorohexyloxy)benzoyl)oxy]phenyl}acrylate-   2-(2,4-Diaminophenyl)ethyl    (2E)3-{4-[(4-(5,5,6,6,6-pentafluorohexyl)benzoyl)oxy]phenyl}acrylate-   2-(2,4-Diaminophenyl)ethyl    (2E)3-{4-[(4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxy}phenyl}acrylate-   2-(2,4-Diaminophenyl)ethyl    (2E)3-{4-[(3-fluoro-4-(4,4,4-trifluorobutoxy)benzoyl)    oxy]phenyl}acrylate-   2-(2,4-Diaminophenyl)ethyl    (2E)3-{4-[(4-(5,5,5-trifluoropentoxy)benzoyl)oxy]phenyl}acrylate-   2-(2,4-Diaminophenyl)ethyl    (2E)3-{4-[(3,4-di(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate-   2-(2,4-Diaminophenyl)ethyl    (2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy    carbonyl)phenoxy)carbonyl]phenyl}acrylate-   2-(2,4-Diaminophenyl)ethyl    (2E)3-{4-[(4-[(4,4,4-trifluorobutoxy)carbonyl]amino)    benzoyl]oxy}phenyl}acrylate.-   2-(2,4-Diaminophenyl)ethyl    (2E)3-{4-[(4-[(4,4,5,5,5-pentafluoropentoxy)carbonyl]amino)    benzoyl]oxy}phenyl}acrylate-   2-(2,4-Diaminophenyl)ethyl    (2E)3-{4-[(3-methoxy-4-trifluoromethoxybenzoyl)oxy]phenyl}acrylate-   2-(2,4-Diaminophenyl)ethyl (2E)3-{4-[(3-methoxy    4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}acrylate-   2-(2,4-Diaminophenyl)ethyl (2E)3-{4-[(3-methoxy    4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate-   2-(2,4-Diaminophenyl)ethyl (2E)3-{4-[(3-methoxy    4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}acrylate-   2-(2,4-Diaminophenyl)ethyl (2E)3-{4-[(3-methoxy    4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}acrylate-   2-(2,4-Diaminophenyl)ethyl (2E)3-{4-[(3-methoxy    4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylate-   2-(2,4-Diaminophenyl)ethyl (2E)3-{4-[(3-methoxy    4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxy}phenyl}acrylate-   2-(2,4-Diaminophenyl)ethyl    (2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]-3-methoxy    phenyl}acrylate-   2-(2,4-Diaminophenyl)ethyl    (2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]-3-methoxyphenyl}acrylate-   2-(2,4-Diaminophenyl)ethyl (2E)3-{4-[(4-(4, 4, 5, 5,    5-pentafluoropentoxy)benzoyl)oxy]-3-methoxyphenyl}acrylate-   2-(2,4-Diaminophenyl)ethyl    (2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]-3-methoxyphenyl}acrylate-   2-(2,4-Diaminophenyl)ethyl    (2E)3-{4-[(4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxy}-3-methoxyphenyl}acrylate-   2-(2,4-Diaminophenyl)ethyl    (2E)3-{4-[(4-(4,4,4-trifluorobutoxy)phenoxy)carbonyl]phenyl}acrylate-   2-(2,4-Diaminophenyl)ethyl    (2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)phenoxy)carbonyl]phenyl}acrylate-   2-(2,4-Diaminophenyl)ethyl    (2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)phenoxy)carbonyl]phenyl}acrylate-   2-(2,4-Diaminophenyl)ethyl    (2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)phenoxy)carbonyl]phenyl}acrylate-   3-(3,5-Diaminophenyl)propyl    (2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}acrylate-   3-(3,5-Diaminophenyl)propyl    (2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}acrylate-   3-(3,5-Diaminophenyl)propyl    (2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate-   3-(3,5-Diaminophenyl)propyl    (2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}acrylate-   3-(3,5-Diaminophenyl)propyl    (2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}acrylate-   3-(3,5-Diaminophenyl)propyl    (2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylate-   3-(3,5-Diaminophenyl)propyl    (2E)3-{4-[(4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxy}phenyl}acrylate    3-(2,4-Diaminophenyl)propyl    (2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate-   3-(2,4-Diaminophenyl)propyl    (2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}acrylate-   3-(2,4-Diaminophenyl)propyl    (2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylate-   3-(2,4-Diaminophenyl)propyl    (2E)3-{4-[(4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxy}phenyl}acrylate-   6-(2,4-Diaminophenyl)hexyl    (2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate-   6-(2,4-Diaminophenyl)hexyl    (2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}acrylate-   6-(2,4-Diaminophenyl)hexyl    (2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylate

EXAMPLE 5 Synthesis Preparation of 2,2-bis(4-aminobenzyl)-1,3di[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol 5.1 Preparation of2,2-dimethyl-5,5-bis(4-nitrobenzyl)-1,3-dioxane-4,6-dione

15.0 g (69.4 mmol) of 4-nitrobenzylbromide and 5.00 g (34.7 mmol) ofMeldrum's acid are dissolved in 100 ml 2-butanone. 4.40 g (104.1 mmol)potassium carbonate are added, the resulting suspension is heated to 50°C. and allowed to react for 2.5 hours. After cooling to roomtemperature, 100 ml water are added. The product is collected byfiltration and washed with a lot of water. 12.3 g (85%) of2,2-dimethyl-5,5-bis(4-nitrobenzyl)-1,3-dioxane-4,6-dione as yellowishpowder is used without further purification.

5.2 Preparation of 2,2-bis(4-nitrobenzyl)malonic acid

2.185 g (52.07 mmol) of lithium hydroxide are added to a suspension of10.79 g (26.04 mmol) of2,2-dimethyl-5,5-bis(4-nitrobenzyl)-1,3-dioxane-4,6-dione and 110 mlmixture of tetrahydrofurane:water 9:1. The mixture is subsequentlyallowed to react for 21.5 hours at 25° C., added to 500 ml water andacidified to pH=1 with 20 ml hydrochloric acid 3N. The mixture ispartitioned between water and ethyl acetate; the organic phase is washedrepeatedly with water, dried over sodium sulfate, filtered andconcentrated by rotary evaporation. The residue 9.54 g (98%) of2,2-bis(4-nitrobenzyl)malonic acid as white powder is used withoutfurther purification.

5.3 Preparation of 2,2-bis(4-nitrobenzyl)-1,3-propandiol

4.00 g (10.69 mmol) 2,2-bis(4-nitrobenzyl)malonic acid are dissolved in40 ml tetrahydrofuran and added dropwise in a the course of 2 hours to64.1 ml (64.1 mmol) of a borane-tetrahydrofuran complex 1.0 M solutionin tetrahydrofuran. After 19 hours at 25° C., 50 ml water are carefullyadded. The reaction mixture is then partitioned between ethyl acetateand water; the organic phase is washed repeatedly with water, dried oversodium sulfate, filtered and concentrated by rotary evaporation. Theresidue, 3.77 g (97%) of 2,2-bis(4-nitrobenzyl)-1,3-propandiol as whitepowder is used without further purification.

5.4 Preparation 2,2-bis(4-nitrobenzyl)-1,3di[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

1.76 g (5.07 mmol) of 2,2-bis(4-nitrobenzyl)-1,3-propandiol, 4.00 g(10.14 mmol) of(2E)-3-(4-{[4-(4,4,4-trifluorobutoxy)benzoyl]oxy}phenyl)acrylic acid,124 mg (1.01 mmol) of 4-Dimethylaminopyridine are dissolved in 100 ml ofdichloromethane. 2.14 g (11.16 mmol) ofN-(3-Dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (EDChydrochloride) are added at 0° C. The solution is stirred for 1 h at 0°C. and allowed to stir at room temperature overnight. After 22 hours atroom temperature the reaction mixture is partitioned betweendichloromethane and water. The organic phase is washed repeatedly withwater, dried over sodium sulphate, filtered and concentrated by rotaryevaporation. Chromatography of the residue on 150 g silica gel usingtoluene:ethyl acetate 9:1 as eluant to yield 2.20 g2,2-bis(4-nitrobenzyl)-1,3di[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol as white crystals.

5.5 Preparation of 2,2-bis(4-aminobenzyl)-1,3di[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2.20 g (2.00 mol) of 2,2-bis(4-nitrobenzyl)-1,3di[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol are dissolved in a mixture of 25 ml of N,N-dimethylformamideand 3 ml water. 3.25 g (12.01 mmol) ferric chloride hexahydrate areadded. 1.31 g (20.02 mmol) Zinc powder are added portionwise within 40min. The mixture is allowed to react for 2 hours. The reaction mixtureis then partitioned between ethyl acetate and water and filtered. Theorganic phase is washed repeatedly with water, dried over sodiumsulfate, filtered and concentrated by rotary evaporation. Chromatographyof the residue on 100 g silica gel using toluene:ethyl acetate 1:1 aseluant and crystallization form ethylacetate:hexane mixture to yield1.20 g 2,2-bis(4-aminobenzyl)-1,3di[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

The following diamines are synthesized in an analogous manner:

-   2,2-bis(4-aminobenzyl)-1,3    di[(2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2,2-bis(4-aminobenzyl)-1,3    di[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2,2-bis(4-aminobenzyl)-1,3    di[(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2,2-bis(4-aminobenzyl)-1,3    di[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2,2-bis(4-aminobenzyl)-1,3    di[(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2,2-bis(4-aminobenzyl)-1,3    di[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2,2-bis(4-aminobenzyl)-1,3    di[(2E)3-{4-[(4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxy}phenyl}prop-2-enoyl]    propanediol-   2,2-bis(4-aminobenzyl)-1,3    di[(2E)3-{4-[(3-methoxy-4-trifluoromethoxybenzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2,2-bis(4-aminobenzyl)-1,3 di[(2E)3-{4-[(3-methoxy    4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2,2-bis(4-aminobenzyl)-1,3 di[(2E)3-{4-[(3-methoxy    4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2,2-bis(4-aminobenzyl)-1,3 di[(2E)3-{4-[(3-methoxy    4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2,2-bis(4-aminobenzyl)-1,3 di[(2E)3-{4-[(3-methoxy    4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2,2-bis(4-aminobenzyl)-1,3 di[(2E)3-{4-[(3-methoxy    4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2,2-bis(4-aminobenzyl)-1,3 di[(2E)3-{4-[(3-methoxy    4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxy}phenyl}prop-2-enoyl]    propanediol-   2,2-bis(4-aminobenzyl)-1,3    di[(2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]    propanediol-   2,2-bis(4-aminobenzyl)-1,3    di[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]    propanediol-   2,2-bis(4-aminobenzyl)-1,3    di[(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]-3-methoxy    phenyl}prop-2-enoyl] propanediol-   2,2-bis(4-aminobenzyl)-1,3    di[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]    propanediol-   2,2-bis(4-aminobenzyl)-1,3    di[(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]    propanediol-   2,2-bis(4-aminobenzyl)-1,3    di[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]    propanediol-   2,2-bis(4-aminobenzyl)-1,3    di[(2E)3-{4-[(4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxy}-3-methoxyphenyl}prop-2-enoyl]    propanediol-   2,2-bis(4-aminobenzyl)-1,3    di[(2E)3-{4-[(4-trifluoromethoxyphenoxy)carbonyl]phenyl}prop-2-enoyl]    propanediol-   2,2-bis(4-aminobenzyl)-1,3    di[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]    propanediol-   2,2-bis(4-aminobenzyl)-1,3    di[(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]    propanediol-   2,2-bis(4-aminobenzyl)-1,3    di[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]    propanediol-   2,2-bis(4-aminobenzyl)-1,3    di[(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]    propanediol-   2,2-bis(4-aminobenzyl)-1,3    di[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]    propanediol

EXAMPLE 6 Synthesis Preparation of6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl3,5-Diamino-4-[6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyloxy]benzoate6.1 Preparation of6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl3,5-dinitro-4-[6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyloxy]benzoate

6.50 g (11.67 mmol) of 6-hydroxyhexyl4-(6-hydroxyhexyloxy)-3,5-dinitrobenzoate, 9.67 g (24.53 mmol) of(2E)-3-(4-{[4-(4,4,4-trifluorobutoxy)benzoyl]oxy}phenyl)acrylic acid,290 mg (2.34 mmol) of 4-Dimethylaminopyridine are dissolved in 100 ml ofdichloromethane. 5.14 g (26.87 mmol) ofN-(3-Dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (EDChydrochloride) are added at 0° C. The solution is stirred for 1 h at 0°C. and allowed to stir at room temperature overnight. After 22 hours atroom temperature the reaction mixture is partitioned betweendichloromethane and water. The organic phase is washed repeatedly withwater, dried over sodium sulphate, filtered and concentrated by rotaryevaporation. Chromatography of the residue on 500 g silica gel usingtoluene:ethyl acetate 95:5 as eluant and crystallization form ethylacetate:hexane mixture to yield 7.70 g of6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl3,5-dinitro-4-[6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyloxy]benzoateas yellow crystals

6.2 Preparation of6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl3,5-Diamino-4-[6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyloxy]benzoate

7.70 g (6.5 mol) of6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl3,5-dinitro-4-[6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyloxy]benzoate are dissolved in amixture of 90 ml of N,N-dimethylformamide and 7 ml water. 10.6 g (39.2mmol) ferric chloride hexahydrate are added. 4.27 g (65.36 mmol) Zincpowder are added portionwise within 40 min. The mixture is allowed toreact for 2 hours. The reaction mixture is then partitioned betweenethyl acetate and water and filtered. The organic phase is washedrepeatedly with water, dried over sodium sulfate, filtered andconcentrated by rotary evaporation. Chromatography of the residue on 200g silica gel using toluene:ethyl acetate 2:1 as eluant andcrystallization form methanol:ethyl acetate mixture to yield 4.92 g6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl3,5-Diamino-4-[6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyloxy]benzoateas colorless crystals.

EXAMPLE 7 Synthesis 7.1 Preparation of4,4′-Dinitro-1,1′-biphenyl-2,2′-dicarboxylic acid

30.0 g (120.13 mmol) Diphenic acid are dissolved at room temperature in469 g (4.59 mol) concentrated sulfuric acid (96%). The solution iscooled to −15° C. and a mixture of 92.4 g (1.011 mol) concentratednitric acid (69%) and 12.0 g (0.117 mol) concentrated sulfuric acid(96%) is added slowly so that the mixture temperature is maintainedbelow 0° C. After the addition the solution is allowed to react at roomtemperature for 24 h. After the mixture is poured onto crushed ice, theprecipitate that formed i collected by filtration, washed with water anddried at room temperature under vacuum for 10 h.

7.2 Preparation of 2,2′-bis(hydroxymethyl-4,4′-Dinitro 1,1′-biphenyl

3.6 g (10.83 mmol) 4,4′-Dinitro-1,1′-biphenyl-2,2′-dicarboxylic acid aredissolved in 25 ml tetrahydrofuran and added dropwise in a the course of1 hours to 65 ml (65.02 mmol) of a borane-tetrahydrofuran complex 1.0 Msolution in tetrahydrofuran. After 19 hours at 25° C., 50 ml water arecarefully added. After 1 h the solution is acidified to pH=1-2 with 10ml 1N HCl solution and allowed to stirred for 30 min. The reactionmixture is then partitioned between ethyl acetate and water; the organicphase is washed repeatedly with water, dried over sodium sulfate,filtered and concentrated by rotary evaporation. The residue, 4.2 g of2,2′-bis(hydroxymethyl-4,4′-Dinitro 1,1′-biphenyl as white powder isused without further purification.

7.3 Preparation of2,2′-bis[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl4,4′-Dinitro 1,1′-biphenyl

3.92 g (12.8 mmol) of 2,2′-bis(hydroxymethyl-4,4′-Dinitro 1,1′-biphenyl,13.20 g (33.5 mmol) of(2E)-3-(4-{[4-(4,4,4-trifluorobutoxy)benzoyl]oxy}phenyl)acrylic acidprepared according to example 1, 0.630 mg (5.15 mmol) of4-Dimethylaminopyridine are dissolved in 200 ml of dichloromethane. 6.91g (11.16 mmol) of N,N′-dicyclohexylcarbodiimide are added at 0° C. Thesolution is stirred for 2 h at 0° C. and allowed to stir at roomtemperature overnight. After 22 hours at room temperature the reactionmixture is partitioned between dichloromethane and water. The organicphase is washed repeatedly with water, dried over sodium sulphate,filtered and concentrated by rotary evaporation. Chromatography of theresidue on 150 g silica gel using toluene:ethyl acetate 9:1 as eluant toyield 12.0 g2,2′-bis[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl4,4′-Dinitro 1,1′-biphenyl as white crystals.

7.4 Preparation2,2′-bis[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl4,4′-Diamino 1,1′-biphenyl

2.27 g (2.14 mol) of2,2′-bis[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl4,4′-Dinitro 1,1′-biphenyl are dissolved in a mixture of 40 ml ofN,N-dimethylformamide and 3 ml water. 3.48 g (12.8 mmol) ferric chloridehexahydrate are added. 1.40 g (21.4 mmol) Zinc powder are addedportionwise within 40 min. The mixture is allowed to react for 2 hours.The reaction mixture is then partitioned between ethyl acetate and waterand filtered. The organic phase is washed repeatedly with water, driedover sodium sulfate, filtered and concentrated by rotary evaporation.Chromatography of the residue on 100 g silica gel using toluene:ethylacetate 7:3 as eluant yield 1.74 g2,2′-bis[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl4,4′-Diamino 1,1′-biphenyl as yellowish crystals.

2,2′-bis[(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl4,4′-diamino 1,1′-biphenyl is prepared analogous to example 7 using(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}acrylicacid.

The following diamines are synthesized in an analogous manner:

-   2,2′-bis[(2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}prop-2-enoyl]methyl    4,4′-diamino 1,1′-biphenyl-   2,2′-bis[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl    4,4′-diamino 1,1′-biphenyl-   2,2′-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl    4,4′-diamino 1,1′-biphenyl-   2,2′-bis[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl    4,4′-diamino 1,1′-biphenyl-   2,2′-bis[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl    4,4′-diamino 1,1′-biphenyl-   2,2′-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxy}phenyl]prop-2-enoyl]methyl    4,4′-diamino 1,1′-biphenyl-   2,2′-bis[(2E)3-{4-[(3-methoxy-4-trifluoromethoxybenzoyl)oxy]phenyl}prop-2-enoyl]methyl    4,4′-diamino 1,1′-biphenyl-   2,2′-bis[(2E)3-{4-[(3-methoxy    4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl    4,4′-diamino 1,1′-biphenyl-   2,2′-bis[(2E)3-{4-[(3-methoxy    4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl    4,4′-diamino 1,1′-biphenyl-   2,2′-bis[(2E)3-{4-[(3-methoxy    4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl    4,4′-diamino 1,1′-biphenyl-   2,2′-bis[(2E)3-{4-[(3-methoxy    4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl    4,4′-diamino 1,1′-biphenyl-   2,2′-bis[(2E)3-{4-[(3-methoxy    4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl    4,4′-diamino 1,1′-biphenyl-   2,2′-bis[(2E)3-{4-[(3-methoxy    4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxy}phenyl]prop-2-enoyl]methyl    4,4′-diamino 1,1′-biphenyl-   2,2′-bis[(2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]methyl    4,4′-diamino 1,1′-biphenyl-   2,2′-bis[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]methyl    4,4′-diamino 1,1′-biphenyl-   2,2′-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]-3-methoxy    phenyl}prop-2-enoyl]methyl 4,4′-diamino 1,1′-biphenyl-   2,2′-bis[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]methyl    4,4′-diamino 1,1′-biphenyl-   2,2′-bis[(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]methyl    4,4′-diamino 1,1′-biphenyl-   2,2′-bis[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]methyl    4,4′-diamino 1,1′-biphenyl-   2,2′-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxy}-3-methoxyphenyl]prop-2-enoyl]methyl    4,4′-diamino 1,1′-biphenyl-   2,2′-bis[(2E)3-{4-[(4-trifluoromethoxyphenoxy)carbonyl]phenyl}prop-2-enoyl]methyl    4,4′-diamino 1,1′-biphenyl-   2,2′-bis[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]methyl    4,4′-diamino 1,1′-biphenyl-   2,2′-bis[(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]methyl    4,4′-diamino 1,1′-biphenyl-   2,2′-bis[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)phenoxy)carbonyl]phenyl}prop-2-enoyl    methyl 4,4′-diamino 1,1′-biphenyl-   2,2′-bis[(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]methyl    4,4′-diamino 1,1′-biphenyl-   2,2′-bis[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]methyl    4,4′-diamino 1,1′-biphenyl

EXAMPLE 8 Synthesis Preparation of 2-(2,4-Diaminophenyl)-1,3di[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol 8.1 Preparation of 2-(2,4-Dinitrophenyl)-1,3di[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2.90 g (12.0 mmol) of 2-(4-nitrophenyl)-1,3-propandiol, 9.54 g (24.2mmol) of (2E)-3-(4-{[4-(4,4,4-trifluorobutoxy)benzoyl]oxy}phenyl)acrylicacid. 296 mg (2.42 mmol) of 4-Dimethylaminopyridine are dissolved in 100ml of dichloromethane. 9.20 g (49.0 mmol) ofN-(3-Dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (EDChydrochloride) are added at 0° C. The solution is stirred for 1 h at 0°C. and allowed to stir at room temperature overnight. After 22 hours atroom temperature the reaction mixture is partitioned betweendichloromethane and water. The organic phase is washed repeatedly withwater, dried over sodium sulphate, filtered and concentrated by rotaryevaporation. Chromatography of the residue on 600 g silica gel usingtoluene:ethyl acetate 9:1 as eluant to yield 7.60 g2-(4-nitrophenyl)-1,3di[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol as white crystals.

8.2 Preparation of 2-(2,4-Diaminophenyl)-1,3di[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

7.60 g (7.64 mmol) of 2-(4-nitrophenyl)-1,3di[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol are dissolved in a mixture of 45 ml of N,N-dimethylformamideand 5 ml water. 12.39 g (45.84 mmol) ferric chloride hexahydrate areadded. 4.99 g (76.4 mmol) Zinc powder are added portionwise within 40min. The mixture is allowed to react for 2 hours. The reaction mixtureis then partitioned between ethyl acetate and water and filtered. Theorganic phase is washed repeatedly with water, dried over sodiumsulfate, filtered and concentrated by rotary evaporation. Chromatographyof the residue on 1000 g silica gel using toluene:ethyl acetate 1:1 aseluant and crystallization form ethylacetate:hexane mixture to yield4.30 g of 2-(2,4-Diaminophenyl)-1,3di[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol.

The following diamines are synthesized in an analogous manner:

-   2-(2,4-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2-(2,4-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2-(2,4-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2-(2,4-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2-(2,4-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2-(2,4-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2-(2,4-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxy}phenyl}prop-2-enoyl]    propanediol-   2-(2,4-Diaminophenyl)-1,3    di[(2E)3-{4-[(3-methoxy-4-trifluoromethoxybenzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2-(2,4-Diaminophenyl)-1,3 di[(2E)3-{4-[(3-methoxy    4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2-(2,4-Diaminophenyl)-1,3 di[(2E)3-{4-[(3-methoxy    4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2-(2,4-Diaminophenyl)-1,3 di[(2E)3-{4-[(3-methoxy    4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2-(2,4-Diaminophenyl)-1,3 di[(2E)3-{4-[(3-methoxy    4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2-(2,4-Diaminophenyl)-1,3 di[(2E)3-{4-[(3-methoxy    4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2-(2,4-Diaminophenyl)-1,3 di[(2E)3-{4-[(3-methoxy    4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxy}phenyl}prop-2-enoyl]    propanediol-   2-(2,4-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]    propanediol-   2-(2,4-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]    propanediol-   2-(2,4-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]-3-methoxy    phenyl}prop-2-enoyl] propanediol-   2-(2,4-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]    propanediol-   2-(2,4-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]    propanediol-   2-(2,4-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]    propanediol-   2-(2,4-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxy}-3-methoxyphenyl}prop-2-enoyl]    propanediol-   2-(2,4-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-trifluoromethoxyphenoxy)carbonyl]phenyl}prop-2-enoyl]    propanediol-   2-(2,4-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]    propanediol-   2-(2,4-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]    propanediol-   2-(2,4-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]    propanediol-   2-(2,4-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]    propanediol-   2-(2,4-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]    propanediol-   2-(3,5-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2-(3,5-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2-(3,5-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2-(3,5-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2-(3,5-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2-(3,5-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2-(3,5-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxy}phenyl}prop-2-enoyl]    propanediol-   2-(3,5-Diaminophenyl)-1,3    di[(2E)3-{4-[(3-methoxy-4-trifluoromethoxybenzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2-(3,5-Diaminophenyl)-1,3 di[(2E)3-{4-[(3-methoxy    4-(2,2,2-trifluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2-(3,5-Diaminophenyl)-1,3 di[(2E)3-{4-[(3-methoxy    4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2-(3,5-Diaminophenyl)-1,3 di[(2E)3-{4-[(3-methoxy    4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2-(3,5-Diaminophenyl)-1,3 di[(2E)3-{4-[(3-methoxy    4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2-(3,5-Diaminophenyl)-1,3 di[(2E)3-{4-[(3-methoxy    4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl]    propanediol-   2-(3,5-Diaminophenyl)-1,3 di[(2E)3-{4-[(3-methoxy    4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxy}phenyl}prop-2-enoyl]    propanediol-   2-(3,5-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-trifluoromethoxybenzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]    propanediol-   2-(3,5-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]    propanediol-   2-(3,5-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]-3-methoxy    phenyl}prop-2-enoyl] propanediol-   2-(3,5-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]    propanediol-   2-(3,5-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]    propanediol-   2-(3,5-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)benzoyl)oxy]-3-methoxyphenyl}prop-2-enoyl]    propanediol-   2-(3,5-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-(4,4,4-trifluorobutanoyl)oxy)benzoyl]oxy}-3-methoxyphenyl}prop-2-enoyl]    propanediol-   2-(3,5-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-trifluoromethoxyphenoxy)carbonyl]phenyl}prop-2-enoyl]    propanediol-   2-(3,5-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-(2,2,2-trifluoroethoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]    propanediol-   2-(3,5-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]    propanediol-   2-(3,5-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-(5,5,5-trifluoropentyloxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]    propanediol-   2-(3,5-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]    propanediol-   2-(3,5-Diaminophenyl)-1,3    di[(2E)3-{4-[(4-(1,1,2,2-tetrafluoroethoxy)phenoxy)carbonyl]phenyl}prop-2-enoyl]    propanediol

EXAMPLE 9 Polymersiation Step A (Formation of the Polyamic Acid)

2.25 g (11.47 mmol) of 1,2,3,4-cyclobutantetracarboxylic aciddianhydride is added to a solution of 8.030 g (12.77 mmol) of6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl3,5-Diaminobenzoate in 56.0 ml of tetrahydrofuran. Stirring is thencarried out at 0° C. for 2 hours. Then another 0.255 g (1.30 mmol) of1,2,3,4-cyclobutantetracarboxylic acid dianhydride are added. Themixture is subsequently allowed to react for 21 hours at roomtemperature. The polymer mixture is diluted with 56 ml THF, precipitatedinto 2000 ml diethyl ether and collected by filtration. The polymer isreprecipitated form THF (160 ml) into 3500 ml water to yield, afterdrying at room temperature under vacuum, 9.42 g of Polyamic Acid 1 inthe from of a white powder; [η]=0.50 dL/g

Analogous to EXAMPLE 9 the following diamines are used for thepreparation of Polyamic Acid with 1,2,3,4-cyclobutantetracarboxylic aciddianhydride

6-{[((2E)-3-{4-[(4-(3,3,3-trifluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl3,5-Diaminobenzoate

yield Polyamic acid 2 as white powder; [η]=0.24 dL/g

6-{[((2E)-3-{4-[(3-methoxy4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyll3,5-Diaminobenzoate

yield Polyamic acid 3 as white powder; [η]=0.25 dL/g.

8-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}octyl3,5-Diaminobenzoate

yield Polyamic acid 4 as white powder; [η]=1.09 dL/g.

4-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}butyl3,5-Diaminobenzoate

yield Polyamic acid 5 as white powder; [η]=0.21 dL/g.

2-[2-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethoxy]ethyl3,5-Diaminobenzoate

yield Polyamic acid 6 as white powder; [η]=0.87 dL/g.

2-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}ethyl3,5-Diaminobenzoate

yield Polyamic acid 7 as white powder; [η]=0.48 dL/g.

3-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}propyl3,5-Diaminobenzoate yield

Polyamic acid 8 as white powder; [η]=0.63 dL/g.

6-{[((2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl3,5-Diaminobenzoate

yield Polyamic acid 9 as white powder; [η]=0.26 dL/g.

6-{[((2E)-3-{4-[(4-trifluoromethoxybenzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl3,5-Diaminobenzoate

yield Polyamic acid 10 as white powder; [η]=0.71 dL/g

6-{[((2E)-3-{4-[(4-trifluoromethylbenzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl3,5-Diaminobenzoate

yield Polyamic acid 11 as white powder; [η]=1.21 dL/g

6-{[((2E)-3-{4-[(4-(2,2,3,3-tetrafluoropropoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl3,5-Diaminobenzoate

yield Polyamic acid 12 as white powder; [η]=0.48 dL/g

6-{[((2E)-3-{4-[(4-(2,2,3,3-tetrafluoroethoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl3,5-Diaminobenzoate

yield Polyamic acid 13 as white powder; [η]=0.48 dL/g

3,5-Diaminobenzyl(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}acrylate

yield Polyamic acid 14 as white powder; [η]=0.59 dL/g

3,5-Diaminobenzyl(2E)3-{4-[(4-(4,4,5,5,6,6,6-heptafluorohexyloxy)benzoyl)oxy]phenyl}acrylate

yield Polyamic acid 15 as white powder; [η]=0.20 dL/g

3,5-Diaminobenzyl(2E)3-{4-[(4-(5,5,5-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate

yield Polyamic acid 16 as white powder; [η]=0.38 dL/g

2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate

yield Polyamic acid 17 as white powder; [η]=0.50 dL/g

2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}acrylate

yield Polyamic acid 18 as white powder; [η]=0.27 dL/g

2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-(4,4,5,5,6,6,6-heptafluorohexyloxy)benzoyl)oxy]phenyl}acrylate

yield Polyamic acid 19 as white powder; [η]=0.19 dL/g

2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-(2,2,3,3-tetrafluoroethoxy)benzoyl)oxy]phenyl}acrylate

yield Polyamic acid 20 as white powder; [η]=0.28 dL/g

2,2-bis(4-aminobenzyl)-1,3di[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

yield Polyamic acid 21 as white powder; [η]=0.54 dL/g

2-(2,4-Dinitrophenyl)-1,3di[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

yield Polyamic acid 22 as white powder; [η]=0.17 dL/g

2-(2,4-Dinitrophenyl)-1,3di[(2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

yield Polyamic acid 23 as white powder; [η]=0.16 dL/g

2,2′-bis[(2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl4,4′-Diamino 1,1′-biphenyl

yield Polyamic acid 24 as white powder; [η]=0.55 dL/g

EXAMPLE 10

Analogous to EXAMPLE 9 the following diamines are used for thepreparation of Polyamic Acid with 2,3,5-tricarboxycyclopentylacetic aciddianhydride

3,5-Diaminobenzyl(2E)3-{4-[(4-(5,5,5-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate

yield Polyamic acid 25 as white powder; [η]=0.40 dL/g

2,2-bis(4-aminobenzyl)-1,3di[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

yield Polyamic acid 26 as white powder; [η]=0.47 dL/g

2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate

yield Polyamic acid 27 as white powder; [η]=0.23 dL/g

2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}acrylate

yield Polyamic acid 28 as white powder; [η]=0.14 dL/g

3,5-Diaminobenzyl(2E)3-{4-[(4-(5,5,5-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate

yield Polyamic acid 29 as white powder; [η]=0.45 dL/g

2,2′-bis[(2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl4,4′-Diamino 1,1′-biphenyl

yield Polyamic acid 30 as white powder; [η]=0.30 dL/g

2,2′-bis[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]methyl4,4′-Diamino 1,1′-biphenyl

yield Polyamic acid 31 as white powder; [η]=0.17 dL/g

2-(2,4-Dinitrophenyl)-1,3di[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

2-(2,4-Dinitrophenyl)-1,3di[(2E)-3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol

EXAMPLE 11

Analogous to EXAMPLE 9 the following tetracarboxylic acid dianhydrideare used for the preparation of Polyamic Acid with of6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl3,5-Diaminobenzoate.

4-(2,5-dioxotetrahydrofuran-3-yl)tetrahydronaphthalene-1,2-dicarboxylicaciddianhydride Diaminobenzoate yield Polyamic acid 32 as white powder;[η]=0.15 dL/g.bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride yieldPolyamic acid 33 as white powder; [η]=0.11 dL/g2,3,5-tricarboxycyclopentylacetic acid dianhydride yield Polyamic acid34 as white powder; [η]=0.43 dL/g5-(2,5-dioxotetrahydrofuran-3-yl)-3-methyl-3-cyclohexene-1,2-dicarboxylic-aciddianhydride yield Polyamic acid 35 as white powder; [η]=0.16 dL/g4,4′-(hexafluoroisopropylidene)diphthalic acid dianhydride yieldPolyamic acid 36 as white powder; [η]=0.51 dL/g

EXAMPLE 12

Analogous to EXAMPLE 9 the following tetracarboxylic acid dianhydridemixture are used for the preparation of Polyamic Acid with of6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl3,5-Diaminobenzoate.

A mixture of 1,2,3,4-cyclobutantetracarboxylic acid dianhydride and4-(2,5-dioxotetrahydrofuran-3-yl)tetrahydronaphthalene-1,2-dicarboxylicacid dianhydride 25:75 (mole ratio) yield Polyamic acid 37 as whitepowder; [η]=0.16 dL/g

A mixture of 1,2,3,4-cyclobutantetracarboxylic acid dianhydride and4-(2,5-dioxotetrahydrofuran-3-yl)tetrahydronaphthalene-1,2-dicarboxylicacid dianhydride 1:1 (mole ratio) yield Polyamic acid 38 as whitepowder; [η]=0.20 dL/g

A mixture of 1,2,3,4-cyclobutantetracarboxylic acid dianhydride and4-(2,5-dioxotetrahydrofuran-3-yl)tetrahydronaphthalene-1,2-dicarboxylicacid dianhydride 75:25 (mole ratio) yield Polyamic acid 39 as whitepowder; [η]=0.20 dL/g

A mixture of 1,2,3,4-cyclobutantetracarboxylic acid dianhydride and4-(2,5-dioxotetrahydrofuran-3-yl)tetrahydronaphthalene-1,2-dicarboxylicacid dianhydride 90:10 (mole ratio) yield Polyamic acid 40 as whitepowder; [η]=0.17 dL/g

A mixture of 1,2,3,4-cyclobutantetracarboxylic acid dianhydride and5-(2,5-dioxotetrahydrofuran-3-yl)-3-methyl-3-cyclohexene-1,2-dicarboxylic-aciddianhydride 25:75 (mole ratio) yield Polyamic acid 41 as white powder;[η]=0.16 dL/g

A mixture of 1,2,3,4-cyclobutantetracarboxylic acid dianhydride and5-(2,5-dioxotetrahydrofuran-3-yl)-3-methyl-3-cyclohexene-1,2-dicarboxylic-aciddianhydride 1:1 (mole ratio) yield Polyamic acid 42 as white powder;[η]=0.16 dL/g

A mixture of 1,2,3,4-cyclobutantetracarboxylic acid dianhydride and5-(2,5-dioxotetrahydrofuran-3-yl)-3-methyl-3-cyclohexene-1,2-dicarboxylic-aciddianhydride 75:25 (mole ratio) yield Polyamic acid 43 as white powder;[η]=0.16 dL/g

EXAMPLE 13

Analogous to EXAMPLE 9 a mixture of 1,2,3,4-cyclobutantetracarboxylicacid dianhydride and4-(2,5-dioxotetrahydrofuran-3-yl)tetrahydronaphthalene-1,2-dicarboxylicacid dianhydride 75:25 (mole ratio) and 3,5-Diaminobenzyl(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}acrylatewere used for the preparation to yield Polyamic acid 44 as white powder;[η]=0.17 dL/g

EXAMPLE 14

Analogous to EXAMPLE 9 a mixture of 1,2,3,4-cyclobutantetracarboxylicacid dianhydride and4-(2,5-dioxotetrahydrofuran-3-yl)tetrahydronaphthalene-1,2-dicarboxylicacid dianhydride 75:25 (mole ratio) and 3,5-Diaminobenzyl(2E)3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}acrylate wereused for the preparation to yield Polyamic acid 45 as white powder;[η]=0.24 dL/g

EXAMPLE 15

Analogous to EXAMPLE 9 a mixture of 1,2,3,4-cyclobutantetracarboxylicacid dianhydride and4-(2,5-dioxotetrahydrofuran-3-yl)tetrahydronaphthalene-1,2-dicarboxylicacid dianhydride 75:25 (mole ratio) and 2-(2,4-Diaminophenyl)ethyl(2E)3-{4-[(4-(4,4,5,5,5-pentafluoropentyloxy)benzoyl)oxy]phenyl}acrylateare used for the preparation to yield Polyamic acid 46 as white powder;[η]=0.11 dL/g

EXAMPLE 16

Analogous to EXAMPLE 9 a mixture of 2,2-bis(4-aminobenzyl)-1,3di[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol and6-{[((2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl3,5-Diaminobenzoate 1:1 (mole ratio) and1,2,3,4-cyclobutantetracarboxylic acid dianhydride are used for thepreparation to yield Polyamic acid 47 as white powder; [η]=0.98 dL/g

EXAMPLE 17

Analogous to EXAMPLE 9 a mixture of 2,2-bis(4-aminobenzyl)-1,3di[(2E)-3-{4-[(4-(4,4,4-trifluorobutoxy)benzoyl)oxy]phenyl}prop-2-enoyl]propanediol and 4,4′-Diaminodiphenylmethane 80:20 (mole ratio) and1,2,3,4-cyclobutantetracarboxylic acid dianhydride are used for thepreparation to yield Polyamic acid 48 as white powder; [η]=1.00 dL/g

EXAMPLE 18 Polymerisation Step B (Formation of the Polyimide)

0.50 g of Polyamic Acid No. 1 obtained in above EXAMPLE 9 are dissolvedin 3 ml of 1-methyl-2-pyrrolidon (NMP). Thereto are added 0.28 g (3.57mmol, 4 equivalent) of pyridine and 364 mg (3.57 mmol, 4 equivalent)acetic acid anhydride, and the dehydration and ring closure is carriedout at 80° C. for 2 h. The polymer mixture is diluted with 1.5 ml NMP,precipitated into 100 ml diethyl ether and collected by filtration. Thepolymer is reprecipitated from THF (10 ml) into 200 ml water to yield,after drying at room temperature under vacuum, 0.55 g Polyimide No 1;[η]=0.50 dL/g, Imidization degree ID=100%

Analogous to the polymerization step of EXAMPLE 18 the followingpolyamic acids are used for the preparation of partially imidizatedpolyimide. The imidization degree is adjusted with the ratio of aceticacid anhydride and pyridine.

Polyamic acid 1 with 1.2 equivalent acetic acid anhydride and pyridineyield Polyimide 1 as white powder; [η]=0.23 dL/g, ID=40%.

Polyamic acid 1 with 0.8 equivalent acetic acid anhydride and pyridineyield Polyimide 1 as white powder; [η]=0.26 dL/g, ID=30%.

Polyamic acid 1 with 0.4 equivalent acetic acid anhydride and pyridineyield Polyimide 1 as white powder; [η]=0.27 dL/g, ID=14%.

Polyamic acid 2 yield Polyimide 2 as white powder; [η]=0.24 dL/g,ID=100%

Polyamic acid 5 yield Polyimide 5 as white powder; [η]=0.36 dL/g,ID=100%

Polyamic acid 13 yield Polyimide 14 as white powder; [η]=0.88 dL/g,ID=100%

Polyamic acid 14 yield Polyimide 13 as white powder; [η]=0.48 dL/g,ID=100%

Polyamic acid 15 yield Polyimide 15 as white powder; [η]=0.20 dL/g,ID=100%

Polyamic acid 16 yield Polyimide 16 as white powder; [η]=0.27 dL/g,ID=100%

Polyamic acid 17 yield Polyimide 17 as white powder; [η]=0.29 dL/g,ID=100%

Polyamic acid 18 yield Polyimide 18 as white powder; [η]=0.28 dL/g,ID=100%

Polyamic acid 19 yield Polyimide 19 as white powder; [η]=0.19 dL/g,ID=100%

Polyamic acid 20 yield Polyimide 20 as white powder; [η]=0.28 dL/g,ID=100%

Polyamic acid 21 yield Polyimide 21 as white powder; [η]=0.63 dL/g,ID=100%

Polyamic acid 25 yield Polyimide 25 as white powder; [η]=0.43 dL/g,ID=100%

Polyamic acid 27 yield Polyimide 27 as white powder; [η]=0.20 dL/g,ID=100%

Polyamic acid 28 yield Polyimide 28 as white powder; [η]=0.14 dL/g,ID=60%

Polyamic acid 28 with 1.0 equivalent acetic acid anhydride and pyridineyield Polyimide 28 as white powder; [η]=0.23 dL/g, ID=25%.

Polyamic acid 34 yield Polyimide 34 as white powder; [η]=0.40 dL/g,ID=100%

Polyamic acid 39 yield Polyimide 39 as white powder; [η]=0.21 dL/g,ID=100%

Polyamic acid 44 yield Polyimide 44 as white powder; [η]=0.14 dL/g,ID=100%

Polyamic acid 45 yield Polyimide 45 as white powder; [η]=0.12 dL/g,ID=100%

EXAMPLE 19 Preparation of an Orientation Layer for Vertical Alignmentwith Non-Polarized UV Light

A 4% solution of LPP (see molecular structure on FIG. 1) in a solventmixture of N-Methyl-2-Pyrrolidone (NMP) and Butylglycol (BC) in a ratioof 1:9 by weight was prepared. This LPP solution was filtered over a 2μm Teflon filter and applied to two indium tin oxyde (ITO) coatedrectangular glass plates by spin coating at 1350 rpm for 30 seconds. Theresulting films were then pre-dried for 5 minutes at 130° C. and furtherpost-baked for 40 minutes at 200° C. Both ITO covered glass plates wereirradiated with non-polarised UV light at a dose of 48 mJ/cm². Thedirection of incidence of the light being inclined by 10° relative tothe plate normal and the incidence plane was parallel to the short sideof the substrate. The two irradiated plates were used to build a cell of20 μm spacing in an anti-parallel manner such that the irradiatedsurfaces were facing each other. The cell was then capillary filled withliquid crystal mixture MLC6610 from Merck in the isotropic phase at 105°C. The cell was then gradually cooled down at a rate of 0.1° C./min fromT=105° C. to T=85° C. and at a rate of 2 C/min from T=85° C. to roomtemperature. When arranged between crossed polarisers, the cell appeareduniformly black for every angle between the short edge of the cell andthe polariser transmission axis, as long as viewed from the vertical. Inconclusion, the liquid crystal mixture was aligned homeotropically.

When the short edge of the cell was set at 45° to the polariser axis andan AC voltage of 7V and 90 Hz was applied, the liquid crystals switchedand caused the cell to appear green (high order birefringence). Nodefects or tilt domains were observed. Brightness and colour of theswitched cell changed asymmetrically when viewed from opposite, butequal oblique angles along a plane parallel to the short edge of thecell. Contrary, no asymmetry was found when viewed obliquely fromopposite angles within a plane parallel to the long edge of the cell.When the switched cell with its short edge was aligned parallel orperpendicular to one of the polariser transmission axes the cellappeared dark again. From above observations we concluded that LCalignment capability was induced in the thin film on the substrate dueto irradiation with slantwise incident non-polarized light. Theazimuthal alignment direction was parallel to the plane of incidence ofthe non-polarized uv-light.

From tilt angle evaluation by means of the crystal rotation method atilt angle value of 89.2° with respect to the substrate surface wasobtained. The direction of the LC molecules was in between the surfacenormal and the direction of the incident light.

EXAMPLE 20 Production of an Orientation Layer Having a Defined Angle ofTilt with Unpolarized UV Light

The same type of experiment has been done with the same LPP, except thatthe direction of incidence of the light was inclined by 40° relative tothe plate normal. The azimuthal alignment direction was parallel to theplane of incidence of the non-polarized UV-light. From tilt angleevaluation by means of the crystal rotation method a tilt angle value of88.65° with respect to the substrate surface was obtained. The directionof the LC molecules was in between the surface normal and the directionof the incident light.

COMPARATIVE SYNTHESIS EXAMPLE 1

Analogous to example 2 16-{[((2E)-3-{4-[(4-butoxybenzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl3,5-Diaminobenzoate were synthesized.

Comparative Polymerisation 1

The preparation is carried out analogously to Synthesis EXAMPLE 9 using920.2 mg (1.683. mmol)6-{[((2E)-3-{4-[(4-butoxybenzoyl)oxy]phenyl}prop-2-enoyl)oxy]}hexyl3,5-Diaminobenzoate, 330.1 mg 1.683 mmol)1,2,3,4-cyclobutantetracarboxylic acid dianhydride to yield 1.01 gComparative Polyamic Acid 1; [η]=0.25 dL/g

COMPARATIVE SYNTHESIS EXAMPLE 2

Analogous to example 3 3,5-Diaminobenzyl(2E)3-{4-[(4-pentyloxy)benzoyl]oxy}phenyl}acrylate are synthesized.

Comparative Polymerisation 2

The preparation is carried out analogously to Synthesis EXAMPLE 9 using1.0390 g (2.15 mmol) 3,5-Diaminobenzyl(2E)3-{4-[(4-pentyloxy)benzoyl]oxy}phenyl}acrylate, 422.2 mg (2.15 mmol)1,2,3,4-cyclobutantetracarboxylic acid dianhydride to yield 1.349 gComparative Polyamic Acid 2; [η]=0.87 dL/g

Example for the Production of an orientation layer having a definedangle of tilt 2% solution of Polyamic acid 1 in cyclopentanone isfiltered over a 0.2 μm Teflon filter and applied to a glass plate, whichhas been coated with indium-tin oxide (ITO), in a spin-coating apparatusat 3000 rev./min. in the course of 60 seconds. The resulting film isthen predried for 15 minutes at 130° C. and then imidized for 1 hour at200° C. to form a polyimide film. The so obtained LPP film is irradiatedfor 30 mJ/cm2 with linearly polarised UV light, the direction ofincidence of the light being inclined by 20° to 40° relative to theplate normal. The direction of polarisation of the light was kept in theplane defined by the direction of incidence of the light and the platenormal. From both plates a cell of 20 μm spacing is built such that theilluminated surfaces are facing each other and the previous polarisationdirections of illumination are parallel. The cell is then filled withliquid crystal mixture MLC6609 from Merck in the isotropic phase at 100°C. The cell is then gradually cooled to room temperature at a rateranging from 0.1° C./min to 2 C/min. Between crossed polarisers auniformly oriented liquid crystal layer is observed. The tilt angle ofthis parallel cell, by crystal rotation method, was 88.7°.

Example for the Determination of the Voltage Holding Ratio (VHR)

Two glass plates coated in accordance with the above example areirradiated perpendicularly during 4 minutes with linearly polarised UVlight. From both plates a cell of 10 μm spacing is built such that theilluminated surfaces were facing each other and the previouspolarisation directions of illumination are parallel. This cell is thenmaintained at 120° C. under high vacuum for 14 hours and thereafterfilled with TFT liquid crystal mixture MLC6610 from Merck in vacuum atroom temperature. Between crossed polarisers a uniformly oriented liquidcrystal layer is observed. Prior to testing the voltage holding ratio(VHR) the cell is first subjected to ageing for 50 hours at 120 C Thevoltage decay V (at T=20 ms) of a voltage surge of 64 μs with V₀ (V att=0)=0.2 V is then measured over a period of T=20 ms. The voltageholding ratio then determined, given by VHR=V_(rms)(t=T)/V₀.

Results VHR = V_(rms)(t = T)/V₀ VHR = V_(rms)(t = T)/V₀ at roomtemperature at 80° C. Polyamic acid 1 97% 92% Comparative Polyamic 85%62% acid 1 Polyamic acid 6 99% 93% Comparative Polyamic 99% 71% acid 2Blend between 95% 92% Polyamic acid 1 and Polyimide 1 (75:25 Weightratio)

1. Diamine compound of formula (I):

wherein, A represents an unsubstituted or substituted carbocyclic orheterocyclic aromatic group selected from a monocyclic ring of five orsix atoms, two adjacent monocyclic rings of five or six atoms, abicyclic ring system of eight, nine or ten atoms, or a tricyclic ringsystem of thirteen or fourteen atoms; and wherein the following compoundresidue of formula (I), the compound of formula (Ia)

represents a straight-chain or branched C₁-C₁₆fluoralkyl group, whereinF is fluorine, and x₁ is an integer from 1 to 15, B represents astraight-chain or branched C₁-C₁₆alkyl group, which is in addition toits fluorine unsubstituted or substituent(s) substituted bydi-(C₁-C₁₆alkyl)amino, C₁-C₆alkyloxy, nitro, cyano and/or chlorine; andwherein one or more —CH₂— group may independently from each other bereplaced by a linking group; D represents an unsubstituted orsubstituted, aliphatic, aromatic and/or alicyclic diamine group havingfrom 1 to 40 carbon atoms, E represents an aromatic group, an oxygenatom, a sulphur atom, —NH—, —N(C₁-C₆alkyl)-, —CR²R³, wherein R² and R³are independently from each other hydrogen or a cyclic, straight-chainor branched, substituted or unsubstituted C₁-C₂₄alkyl, wherein one ormore —CH₂— group(s) may be independently from each other replaced by alinking group, and with the proviso that at least one of R² and R³ isnot hydrogen; S¹, S² each independently from each other represents aspacer unit; X, Y each independently from each other representshydrogen, fluorine, chlorine, cyano, unsubstituted or with fluorinesubstituted C₁-C₁₂alkyl, in which one or more —CH₂— groups may bereplaced by a linking group; n, n1 each independently from each otherrepresents 1, 2, 3 or 4, with the proviso that if n is 2, 3, or 4, eachA, B, x₁, D, E, S¹, S², X, Y are identical or different; and if n1 is 2,3 or 4 each B, x₁ is identical or different.
 2. Diamine compoundaccording to claim 1, wherein the linking group is selected from —O—,—CO, —CO—O—, —O—CO—,

—NR¹—, —NR¹—CO—, —CO—NR¹—, —NR¹—CO—O—, —O—CO—NR¹—, —NR¹—CO—NR¹—,—CH═CH—, —C≡C—, —O—CO—O—, and —Si(CH₃)₂—O—Si(CH₃)₂—, and wherein: R¹represents a hydrogen atom or C₁-C₆alkyl; with the proviso that oxygenatoms of linking groups are not directly linked to each other. 3.Diamine compound according to claim 1, wherein the spacer unit is asingle bond, a cyclic, straight-chain or branched, substituted orunsubstituted C₁-C₂₄alkylen, wherein one or more —CH₂— group mayindependently from each other be replaced by a linking group asdescribed in claim 2 and/or an non-aromatic, aromatic, unsubstituted orsubstituted carbocyclic or heterocyclic group connected via bridginggroups.
 4. Diamine compound according to claim 3, wherein the bridginggroup is selected from —CH(OH)—, —CO—, —CH₂(CO)—, —SO—, —CH₂(SO)—,—SO₂—, —CH₂(SO₂)—, —COO—, —OCO—, —COCF₂—, —CF₂CO, —S—CO—, —CO—S—, —SOO—,—OSO—, —SOS—, —O—CO—O, —CH₂—CH₂—, —OCH₂—, —CH₂O—, —CH═CH—, —C≡C—,—CH═CH—COO—, —OCO—CH═CH—, —CH═N—, —C(CH₃)═N—, —N═N— or a single bond; ora cyclic, straight-chain or branched, substituted or unsubstitutedC₁-C₂₄alkylen, wherein one or more —CH₂— group may independently fromeach other be replaced independently from each other by a linking groupas described in claim
 2. 5. Diamine compound according to any of thepreceding claims, wherein D is preferably selected from formula (III):H(R⁵)N-(Sp¹)_(k1)-(X¹)_(t1)-(Z³-C³)_(a3)-(Z⁴-C⁴)_(a4)—(X²)_(t2)-(Sp²)_(k2)-N(R⁶)H  (III)wherein: R⁵, R⁶ each independently from each other represents a hydrogenatom or C₁-C₆alkyl; Sp¹, Sp² each independently from each otherrepresent an unsubstituted or substituted straight-chain or branchedC₁-C₂₀alkylene, in which one or more —CH₂-group may independently fromeach other be replaced by a linking group, and k¹, k² each independentlyis an integer having a value of 0 or 1; and X¹, X² each independentlyrepresents a linking spacer, and t¹, t² each independently is an integerhaving a value of 0 or 1; and C³, C⁴ each independently represents anon-aromatic, aromatic, substituted or unsubstituted carbocyclic orheterocyclic group, which may have a side chain T, and Z³ represents abridging group; and Z⁴ represents a substituted or unsubstitutedstraight-chain or branched C₁-C₂₀alkylene group, in which one or more—CH₂— group may independently from each other be replaced by anon-aromatic, aromatic, unsubstituted or substituted carbocyclic orheterocyclic group; and/or a heteroatom and/or by a bridging group; anda₃, a₄ are independently integers from 0 to 3, such that a₃+a₄≦4; andwherein D is at least once linked to at least one group S¹ in formula(I) via group Sp¹ and/or group Sp²; and/or linked via at least onenon-aromatic, aromatic, substituted or unsubstituted carbocyclic orheterocyclic group of C³ and/or group of C⁴, and/or linked via at leastone side chain T of group C⁴ and/or group of C³; and/or linked via groupZ⁴; and at least one of k¹, k², a³ and a⁴ is not equal to zero; andwherein linking group is as defined in claim 2, and bridging group is asdefined in claim
 4. 6. Diamine compound according to claim 5, whereinthe side chain, T, represents a substituted or unsubstitutedstraight-chain or branched C₁-C₂₀alkylene group, in which one or more—CH₂— group(s) may independently from each other be replaced by anon-aromatic, aromatic, unsubstituted or substituted carbocyclic orheterocyclic group, or a heteroatom and/or by a bridging group, which isat least once linked to at least once group S¹ in formula (I) asdescribed in claim
 1. 7. Diamine compound according to claims 5 and 6,wherein C³, C⁴ independently from each other are selected from acompound of group G², wherein G² is:

wherein: “-” denotes the connecting bonds of C³ and C⁴ to the adjacentgroups of compound of formula (III) as described in claim 5; and L is—CH₃, —COCH₃, —OCH₃, nitro, cyano, halogen, CH₂═CH—, CH₂═C(CH₃)—,CH₂═CH—(CO)O—, CH₂═CH—O—, —NR⁵R⁶, CH₂═C(CH₃)—(CO)O—, CH₂═C(CH₃)—O—,wherein: R⁵, R⁶ each independently from each other represents a hydrogenatom or C₁-C₆alkyl; T represents a substituted or unsubstitutedstraight-chain or branched C₁-C₂₀alkylene group, in which one or more—CH₂— group may independently from each other be replaced by anon-aromatic, aromatic, unsubstituted or substituted carbocyclic orheterocyclic group, or a heteroatom and/or by a bridging group; m is aninteger from 0 to 2; u₁ is an integer from 0 to 4, with the proviso thatm+u₁ is ≦4; and u₂ is an integer from 0 to 3; with the proviso that m+u₂is ≦3; and u₃ is an integer from 0 to 2; with the proviso that m+u₃ is≦2.
 8. Diamine compound according to any of the preceding claims,wherein D is a selected the group of the following compounds:

wherein L, L₁, L₂ and L₃ are indepentyl from each other —CH₃, —COCH₃,—OCH₃, nitro, cyano, halogen, CH₂═CH—, CH₂═C(CH₃)—, CH₂═CH—(CO)O—,CH₂═CH—O—, —NR⁵R⁶, CH₂═C(CH₃)—(CO)O— or CH₂═C(CH₃)—O—, T, T₁, T₂ and T₃are indepentyl from each other a substituted or unsubstitutedstraight-chain or branched C₁-C₂₀alkylene group, in which one or more—CH₂— group(s) may independently from each other be replaced by anon-aromatic, aromatic, unsubstituted or substituted carbocyclic orheterocyclic group, and/or a heteroatom and/or by a bridging group; “-”is a single bond, q is an integer of 1 or 2; and q1, q2 and q3 areindepentyl from each other an integer from 0 to 2; m is an integer of 1or 2; m1, m2 and m3 are indepentyl from each other an integer from 0 to2; u₃, u_(3′), and u_(3″) are indepentyl from each other an integer from0 to 2; R⁵, R⁶ and Z⁴ are as described above; and wherein D is at leastonce linked to at least one group S¹ in formula (I), as described inclaim 1, via a single bond “-”; or via a side chain T, T₁, T₂ or T₃; orvia group Z⁴; with the proviso that u3+q, or u3+m is ≦4; u3+q1 and/oru3′+q2 or/and u3+m1, or/and u3′+m2, or/and u3″+q3, or/and u3″+m3 is ≦4;q1+q2, and m1+m2; and q1+q2+q3, and m1+m2+m3 is ≧1.
 9. Diamine compoundaccording to any of the preceding claims, wherein the following compoundresidue of compound of formula (I) as described in claim 1

represents a straight-chain or branched C₁-C₁₆fluoralkyl group withterminal units selected from —CF₂H and —CF₃.
 10. Diamine compoundaccording to any of the preceding claims, wherein S¹, S² eachindependently from each other represents a single bond or a cyclic,straight-chain or branched, substituted or unsubstituted C₁-C₂₄alkylen,in which one or more —CH₂— group may independently from each other bereplaced by a linking group, and/or a non-aromatic, aromatic,unsubstituted or substituted carbocyclic or heterocyclic group offormula (IV):-(Z¹-C¹)_(a1)-(Z²-C²)_(a2)-(Z^(1a))_(a3)-  (IV) wherein: C¹, C² eachindependently represents a non-aromatic, aromatic, unsubstituted orsubstituted carbocyclic or heterocyclic group, and Z¹, Z², Z^(1a) eachindependently represents a bridging group, and a₁, a₂, a₃ eachindependently represents an integer from 0 to 3, a₁+a₂+a₃≦6, wherein thebridging groups Z¹, Z^(1a) and Z² are as described in claim
 4. 11.Diamine compound according to any preceding claim, which is a compoundof formulae (VI), (VII), (VIII), (IX), (X), (XI), (XIa) and (XIb)

wherein A, B, x₁, n, n1, D, E, S², S¹, X and Y have the above givenmeanings as in claim 1 and R⁵, R⁶ and Z⁴ have the same meanings as inclaim 5; L is —CH₃, —OCH₃, —COCH₃, nitro, cyano, halogen, CH₂═CH—,CH₂═C(CH₃)—, CH₂═CH—(CO)O—, CH₂═CH—O—, CH₂═C(CH₃)—(CO)O—, orCH₂═C(CH₃)—O—, u₃ is an integer from 0 to
 2. 12. Diamine compoundaccording to any preceding claim, which is a compound of formula (XII)

wherein x₁, B, n, n1, D, E, S¹, X and Y have the above given meanings asin claim 1 and Z¹ has the same meaning as in claim 10, and L, u₁ and u₂have the same meanings as in claim
 7. 13. Diamine compound according toany preceding claim, selected from

wherein S¹ has the above given meaning as in claim and wherein thefollowing compound residue

represents a straight-chain or branched C₁-C₈fluoralkyl group, wherein Fis fluorine, and x₁ is an integer from 1 to 9, B represents astraight-chain or branched C₁-C₈alkyl group, which is unsubstituted orin addition to its fluorine substituent(s) substituted bydi-(C₁-C₁₆alkyl)amino, C₁-C₆alkyloxy, nitro, cyano and/or chlorine; andwherein one or more —CH₂— group may independently be replaced by alinking group selected from —O—, —CO—, —CO—O—, —O—CO—, —NR¹—, —NR¹—CO—,—CO—NR¹— and —CH═CH—, wherein: R¹ represents a hydrogen atom orC₁-C₆alkyl; with the proviso that oxygen atoms are not directly linkedto each other; and wherein the C₁-C₈fluoralkyl group has terminal unitsselected from —CF₂H, —CF₃.
 14. Polymer, copolymer or oligomer comprisingdiamine (I) according to any of the preceding claims, as one basicbuilding block.
 15. Polymer, copolymer or oligomer according to claim14, which is a polyamic acid, polyamic ester, polyimide or a mixture ofpolyamic acid and polyamic ester and/or polyimide.
 16. A process for thepreparation of diamine compound (XII) as defined in claim 12 comprisingcontacting a compound of formula (XIV)

with a dinitro compound of formula (XVI)

and then converting the obtained dinitro compound of formula (XVIa)

in the corresponding diamino compound of formula (XII)

wherein F, x₁, n₁, n, B, D, X, Y, Z¹, L, u₁, u₂ and S¹ have the samemeaning as in claim 11, and wherein D1 has the same meaning as D as inclaim 7, with the proviso that the two amino groups of D are replaced bytwo nitro groups.
 17. Compound of formula (XIV) and compound of formula(XVIa) as defined in claim
 16. 18. Composition comprising at least onediamine (I) and optionally at least one further diamine, which isdifferent from (I) or/and an additive.
 19. Process for the preparationof a polymer, copolymer or oligomer comprising polymerisation of adiamine (I).
 20. Polymer, copolymer or oligomer obtainable by reactionaccording to claim 19 comprising a diamine of compound (I) according toany of the preceding claims.
 21. Polymer, copolymer or oligomeraccording to claim 20 or prepared according to claim 19, which is apolymer gel or a polymer network, copolymer gel or a copolymer network,or an oligomer gel or an oligomer network.
 22. Polymer, copolymer oroligomer according to any of claims 20 or 21 or prepared according toclaim 19, which is able to undergo photocyclization.
 23. Composition,especially a blend, comprising a polymer, copolymer or oligomercomprising at least a diamine (I) according to claim 1 as basic buildingblock, or a polymer, copolymer or oligomer obtainable according to claim20.
 24. Method for the preparation of a polymer, copolymer or oligomeraccording to any of claims 20 or 22 or prepared according to claim 19,wherein in a polycondensation reaction a diamine (I) according to claim1 is reacted with one or more tetracarboxylic acid anhydride, optionallyin the presence of one or more additional other diamines.
 25. Polymer,copolymer or oligomer layer, comprising at least one polymer, copolymeror oligomer according to any of claims 20 or 22 or prepared according toclaim
 19. 26. Method for the preparation of a polymer layer or oligomerlayer, wherein one or more polymers, copolymers or oligomers accordingto any of claims 20 or 22 or prepared according to claim 19 is appliedto a support, and wherein, the polymer or oligomer or polymer mixture oroligomer mixture is treated with aligning light.
 27. Polymer, copolymeror oligomer layer obtainable by the method according to claim
 26. 28.Optical and electro-optical unstructured or structured constructionalelements, preferably liquid crystal display cells, multi-layer andhybrid layer elements, comprising at least one polymer layer, copolymeror oligomer layer according to claim
 27. 29. Orientation layer,comprising at least one polymer layer, copolymer or oligomer layeraccording to claim 27.